1. The preparation method of the high-hardness and high-wear-resistance silver-doped diamond infrared antireflection film material is characterized by comprising the following specific steps of:

step 1, inserting silver rods into the cross section of a graphite target material, and distributing the silver rods at the vertexes and the centroid of an equilateral hexagon concentric with the cross section of the graphite target material to prepare a silver-doped graphite target material;

and 2, putting the potassium bromide sheet into a vacuum cathode arc plasma evaporation cavity, vacuumizing, and plating the film on the potassium bromide sheet by adopting a vacuum cathode arc plasma evaporation method to obtain the high-hardness and high-wear-resistance silver-doped diamond infrared anti-reflection film.

2. The method according to claim 1, wherein the silver rod has a purity of 99.99% in step 1.

3. The method of claim 1, wherein in step 1, the sides of the equilateral hexagons are 0.8 cm.

4. The preparation method according to claim 1, wherein in the step 1, the ratio of the total exposed sectional area of the three silver rods to the exposed sectional area of the graphite is 0.1848: 1.

5. the preparation method according to claim 1, wherein in the step 2, the stainless steel material is ultrasonically cleaned by ethanol for 5-10 minutes, then ultrasonically cleaned by distilled water for 5-10 minutes, and finally ultrasonically cleaned by ethanol with the ultrasonic frequency of 5 Hz.

6. The method according to claim 1, wherein the degree of vacuum in step 2 is 10^-3Pa, and 3000A current.

7. The method according to claim 1, wherein the number of plating in step 2 is 1000 to 2000.

Background

The infrared antireflection film is widely applied to modern optical periods, greatly influences the performance of an optical device, and has very important significance in the field of the optical device. Generally, the infrared antireflection film is prepared by physical vapor deposition, chemical vapor deposition, magnetic co-sputtering, or the like. At present, the modification of the existing infrared antireflection film material and the development of a novel infrared antireflection film material are particularly focused on the infrared transmittance, mechanical strength and other properties of the film material and different working wave bands of the infrared antireflection film.

Graphite as a widely used material has the advantages of wide source, low price, reproducibility and the like, and a diamond-like carbon film prepared from the graphite has development potential and has the problems of obvious carbon-oxygen bond absorption peak and the like although the diamond-like carbon film is hard and wear-resistant and has high infrared transmittance. And the binding force of the material with optical devices such as quartz glass and the like is not high enough, so that the material is difficult to be applied to practice.

The silver noble metal has great potential advantages in the fields of Raman enhancement effect, solar cell refraction layer and the like due to the excellent optical characteristics of the silver noble metal in the range of 200 nm-400 nm, but still has the problems of complex preparation process, low repeatability and high price. And the prepared silver particles have low wear resistance and poor mechanical properties.

Disclosure of Invention

The invention aims to provide a preparation method of a high-hardness and high-wear-resistance silver-doped diamond infrared antireflection film. The method uses a diamond-like film to replace the traditional film, inserts a silver rod into a graphite target, dissolves silver as solute of solid solution, and plates a layer of diamond-like silver-doped film on the surface of a substrate.

The technical scheme for realizing the purpose of the invention is as follows:

the preparation method of the high-hardness and high-wear-resistance silver-doped diamond infrared antireflection film material comprises the following specific steps:

step 1, inserting silver rods into the cross section of a graphite target material, and distributing the silver rods at the vertexes and the centroid of an equilateral hexagon concentric with the cross section of the graphite target material to prepare a silver-doped graphite target material;

and 2, putting the potassium bromide sheet into a vacuum cathode arc plasma evaporation cavity, vacuumizing, and plating the film on the potassium bromide sheet by adopting a vacuum cathode arc plasma evaporation method to obtain the high-hardness and high-wear-resistance silver-doped diamond infrared anti-reflection film.

Preferably, in step 1, the purity of the silver rod is 99.99%.

Preferably, in step 1, the side length of the equilateral hexagon is 0.8 cm.

Preferably, in step 1, the ratio of the sum of the exposed cross-sectional areas of the three silver rods to the exposed cross-sectional area of the graphite is 0.1848: 1.

preferably, in the step 2, ultrasonic cleaning of the stainless steel material is performed for 5-10 minutes by using ethanol, then ultrasonic cleaning is performed for 5-10 minutes by using distilled water, and finally ultrasonic cleaning is performed by using ethanol, wherein the ultrasonic frequency is 5 Hz.

Preferably, in step 2, the vacuum degree is 10^-3Pa, and 3000A current.

Preferably, in the step 2, the number of plating is 1000-2000.

Compared with the prior art, the invention has the following advantages:

(1) the invention adopts the diamond-like carbon film, greatly improves the wear resistance of the film, has strong designability of the diamond-like carbon film, and is easy to adjust the technical application details;

(2) according to the invention, silver is added into the diamond-like carbon film, the silver has nano silver and silver crystal grains of 200nm, on one hand, the nano silver can improve the binding force of the composite film, on the other hand, the silver crystal grains can improve the optical performance of the film, and the infrared transmittance of the diamond-like carbon film is improved by compounding the diamond-like carbon and the silver;

(3) according to the invention, the silver rods are inserted into the carbon target, and the positions of 7 silver rods are strictly controlled, so that uniform and stable nano silver and silver crystal grains are physically and stably deposited on the surface of the substrate in a vapor phase manner, a large silver target does not need to be specially manufactured, the utilization rate of silver is greatly improved, and the cost is saved;

(4) the preparation method is simple, convenient, rapid, cheap, high in repeatability and convenient for large-scale production.

Drawings

FIG. 1(a) is a diagram showing a pair of silver-doped diamond-like films prepared by doping 7 silver rods in example 1, the pair of the films having a thickness of 400 to 4000cm^-1Band infrared transmittance.

FIG. 1(b) is a graph showing a pair of silver-doped diamond-like films prepared by doping 5 silver rods prepared in comparative example 1, the pair of silver-doped diamond-like films being 400 to 4000cm^-1Band infrared transmittance.

FIG. 1(c) A pair of silver-doped diamond-like films of 400 to 4000cm prepared by doping 3 silver rods prepared in comparative example 2^-1Band infrared transmittance.

FIG. 1(d) shows a pair of silver-doped diamond-like films prepared by doping 1 silver rod prepared in comparative example 3, the pair of silver-doped diamond-like films having a thickness of 400 to 4000cm^-1Band infrared transmittance.

FIG. 2 is an XPS analysis of the diamond-like carbon film of example 1.

FIG. 3 is a transmission electron micrograph of the diamond-like carbon film of example 1.

FIG. 4 is an EDS scan of silver in the diamond-like film obtained in example 1.

Fig. 5 is an EDS analysis chart of the diamond-like carbon film of comparative example 1.

Fig. 6 is an EDS analysis chart of silver in the diamond-like thin film obtained in comparative example 2.

Fig. 7 is an EDS analysis chart of the diamond-like thin film of comparative example 3.

FIG. 8 is an infrared absorption chart of comparative example 4.

Detailed Description

The present invention will be described in further detail below with reference to examples and the accompanying drawings.

Example 1

Seven cylindrical silver rods with the length of 5mm and the diameter of 3mm are taken. Inserting silver rods into the cross section of a graphite target material with the length of 10cm and the diameter of 3cm, wherein the silver rods are distributed at the vertexes and the centroids of an equilateral hexagon concentric with the cross section of the graphite and with the side length of 8mm, and the ratio of the total exposed sectional area of the three silver rods to the exposed sectional area of the graphite is 0.0753: 1, preparing the silver-doped graphite target material. Taking a potassium bromide sheet with the square centimeter being about 1, putting the potassium bromide sheet into Vactime-DLC vacuum cathode arc plasma evaporation equipment, vacuumizing, using a graphite target doped with silver, plating films for 2000 times at 5Hz to obtain a film plating material, and carrying out Fourier infrared scanning on the obtained film material.

Comparative example 1

Five cylindrical silver rods with the length of 5mm and the diameter of 3mm are taken. Inserting silver rods into the cross section of a graphite target material with the length of 10cm and the diameter of 3cm, wherein the silver rods are distributed at the top and the centroid of a square with the side length of 8mm concentric with the cross section of the graphite, and the ratio of the total exposed sectional area of the three silver rods to the exposed sectional area of the graphite is 0.0526: 1, preparing the silver-doped graphite target material. Taking a potassium bromide sheet with the square centimeter being about 1, putting the potassium bromide sheet into Vactime-DLC vacuum cathode arc plasma evaporation equipment, vacuumizing, using a graphite target doped with silver, plating films for 2000 times at 5Hz to obtain a film plating material, and carrying out Fourier infrared scanning on the obtained film material.

Comparative example 2

Three cylindrical silver rods with the length of 5mm and the diameter of 3mm are taken. Inserting silver rods into the cross section of a graphite target material with the length of 10cm and the diameter of 3cm, wherein the silver rods are distributed at the vertex of a triangle concentric with the cross section of the graphite and with the side length of 10mm, and the ratio of the total exposed sectional area of the three silver rods to the exposed sectional area of the graphite is 0.0309: 1, preparing the silver-doped graphite target material. Taking a potassium bromide sheet with the square centimeter being about 1, putting the potassium bromide sheet into Vactime-DLC vacuum cathode arc plasma evaporation equipment, vacuumizing, using a graphite target doped with silver, plating films for 2000 times at 5Hz to obtain a film plating material, and carrying out Fourier infrared scanning on the obtained film material.

Comparative example 3

A cylindrical silver rod with the length of 5mm and the diameter of 3mm is taken. And inserting a silver rod into the cross section of the graphite target material with the length of 10cm and the diameter of 3cm at the center of the cross section of the graphite target material. The ratio of the total exposed sectional area of the silver rods to the exposed sectional area of the graphite is 0.0101: 1, preparing the silver-doped graphite target material. Taking a potassium bromide sheet with the square centimeter being about 1, putting the potassium bromide sheet into Vactime-DLC vacuum cathode arc plasma evaporation equipment, vacuumizing, using a graphite target doped with silver, plating films for 2000 times at 5Hz to obtain a film plating material, and carrying out Fourier infrared scanning on the obtained film material.

Comparative example 4

Seven cylindrical copper rods with the length of 5mm and the diameter of 3mm are taken. Inserting silver rods into the cross section of a graphite target material with the length of 10cm and the diameter of 3cm, wherein the silver rods are distributed at the top point and the centroid of an equilateral hexagon concentric with the cross section of the graphite and with the side length of 8mm, and the ratio of the total exposed sectional area of the three copper rods to the exposed sectional area of the graphite is 0.0753: 1, preparing the silver-doped graphite target material. Taking a potassium bromide sheet with the square centimeter being about 1, putting the potassium bromide sheet into Vactime-DLC vacuum cathode arc plasma evaporation equipment, vacuumizing, using a graphite target material doped with copper, plating films for 2000 times at 5Hz to obtain a film plating material, and carrying out Fourier infrared scanning on the obtained film material.

FIG. 1(a) is a diagram showing a pair of silver-doped diamond-like films prepared by doping 7 silver rods in example 1, the pair of the films having a thickness of 400 to 4000cm^-1The transmittance of infrared rays in the wave band is shown in FIG. 1(b), which is 400-4000 cm of a pair of silver-doped diamond-like films prepared by doping 5 silver rods prepared in comparative example 1^-1Wave band infrared transmittance, figure 1(c) silver-doped diamond-like film pair prepared by doping 3 silver rods prepared in comparative example 20cm^-1The transmittance of infrared rays in the wave band is shown in FIG. 1(d) as the transmittance of the silver-doped diamond-like film pair prepared by doping 1 silver rod prepared in the comparative example 3 to 400-4000 cm^-1Band infrared transmittance. As can be seen from FIG. 1, the high-hardness and high-wear-resistance silver-doped diamond infrared antireflection film doped with seven silver rods has the best infrared ray absorption effect, and generally reaches more than 99%.

FIG. 2 is an XPS analysis of the diamond-like film of example 1 showing that the sample contained 2% silver. FIG. 3 is an electron micrograph of the diamond-like thin film of example 1, and it can be seen that the sample contains silver crystals and nano silver particles with a diameter of 400-500 nm. Fig. 4, 5, 6, and 7 are EDS scans of silver in the diamond-like thin films prepared in example 1 and comparative examples 1, 2, and 3, respectively, and it can be seen that nano silver particles are uniformly distributed in the diamond-like thin films. FIG. 8 is an infrared absorption spectrum of comparative example 4. It was found that when silver was replaced with copper, the infrared absorption was increased and the infrared transmittance was decreased.