阅读说明：本技术 适用3.7-4.8μm波段的高光学性能强环境适应性减反膜及其制备方法 (High-optical-performance strong-environmental-adaptability anti-reflection film applicable to 3.7-4.8 mu m wave band and preparation method thereof ) 是由 张友良 李刚 董力 谢启明 吴栋才 彭浪 孙晨 陈晓东 于 2020-12-08 设计创作，主要内容包括：本发明涉及红外镀膜技术领域,尤其涉及适用3.7-4.8μm波段的高光学性能强环境适应性减反膜及其制备方法,包括从下至上的基底层、空气层,和设置于基底层、空气层之间的膜层结构基底层的材料为Ge、Si、ZnS、ZnSe中的一种；膜层结构为多层膜层,从下至上为依次连接的Ge层、ZnS层、Ge层、ZnS层、YbF_3层、MgF_2层、Al_2O_3层、SiO_2层、防水层。可实现同时提升3.7-4.8μm波段红外减反膜的光学性能和膜层环境适应性能,满足新型光学仪器在严苛环境条件下的使用要求。(The invention relates to the technical field of infrared coating, in particular to a high-optical-performance strong-environmental-adaptability antireflection film suitable for a wave band of 3.7-4.8 mu m and a preparation method thereof, wherein the antireflection film comprises a substrate layer, an air layer and a film layer, wherein the substrate layer, the air layer and the film layer are arranged on the substrate layer from bottom to topThe film layer structure substrate layer between the bottom layer and the air layer is made of one of Ge, Si, ZnS and ZnSe; the film layer structure is a multi-layer film layer, and the Ge layer, the ZnS layer, the Ge layer, the ZnS layer and the YbF are sequentially connected from bottom to top 3 Layer, MgF 2 Layer of Al 2 O 3 Layer, SiO 2 Layer, waterproof layer. The optical performance and the film layer environmental adaptability of the infrared antireflection film with the wave band of 3.7-4.8 mu m can be simultaneously improved, and the use requirement of a novel optical instrument under a severe environment condition is met.)

1. The anti-reflection film with high optical performance and strong environmental adaptability and suitable for the wave band of 3.7-4.8 mu m is characterized by comprising a substrate layer, an air layer and a film layer structure arranged between the substrate layer and the air layer from bottom to top; the base layer is made of one of Ge, Si, ZnS and ZnSe; the film structure is a multilayer film, and the Ge layer, the ZnS layer, the Ge layer, the ZnS layer and the YbF are sequentially connected from bottom to top₃Layer, MgF₂Layer of Al₂O₃Layer, SiO₂Layer, waterproof layer.

2. The high optical performance high environmental adaptive antireflection film suitable for use in the wavelength band of 3.7 to 4.8 μm according to claim 1, wherein the thickness of each film layer of the film layer structure is adjusted according to the material of the substrate layer.

3. The anti-reflection film with high optical performance and strong environmental adaptability and suitable for the waveband of 3.7-4.8 μm as claimed in claim 1 or 2, wherein the substrate layer is made of Ge material, and the thickness of each layer of film layer of the film layer structure is as follows: 31.53nm Ge layer, 183.15nm ZnS layer, 59.89nm Ge layer, 94.17nm ZnS layer, YbF₃The layer is 545.00nm MgF₂Layer of 50.00nm, Al₂O₃The layer is 90.00nm, SiO₂The layer is 20.00nm and the waterproof layer is 10 nm.

4. The anti-reflection film with high optical performance and strong environmental adaptability applicable to the waveband of 3.7-4.8 μm as claimed in claim 1 or 2, wherein the substrate layer is made of Si material, and the thickness of each layer of film layer of the film layer structure is as follows in sequence: 98.12nm Ge layer, 207.68nm ZnS layer, 54.01nm Ge layer, 168.58nm ZnS layer and YbF₃The layer is 505.00nm MgF₂Layer of 50.00nm, Al₂O₃The layer is 90.00nm, SiO₂The layer is 20nm and the waterproof layer is 10 nm.

5. The high optical performance and strong environmental adaptability antireflection film for the wavelength band of 3.7-4.8 μm according to claim 1 or 2,the method is characterized in that the substrate layer is made of ZnS material, and the thickness of each layer of film layer of the film layer structure is as follows in sequence: 31.32nm Ge layer, 321.34nm ZnS layer, 30.79nm Ge layer, 352.48nm ZnS layer, YbF₃The layer is 468.00nm MgF₂Layer of 50.00nm, Al₂O₃The layer is 90.00nm, SiO₂The layer is 20nm and the waterproof layer is 10 nm.

6. The anti-reflection film with high optical performance and strong environmental adaptability, applicable to the waveband of 3.7-4.8 μm according to claim 1 or 2, wherein the substrate layer is a ZnSe material, and the thicknesses of the film layers of each film layer of the film layer structure are as follows in sequence: a Ge layer of 37.55nm, a ZnS layer of 300.97nm, a Ge layer of 363.22nm, a ZnS layer of 498.00nm, YbF₃The layer is 498.00nm MgF₂Layer of 50.00nm, Al₂O₃The layer is 90.00nm, SiO₂The layer is 20nm and the waterproof layer is 10 nm.

7. The method for manufacturing the anti-reflection film with high optical performance and strong environmental adaptability and suitable for the wave band of 3.7-4.8 mu m is characterized by comprising the following steps of:

step S1, plating a film layer structure on the surface of the substrate layer, sequentially including a Ge layer, a ZnS layer, a Ge layer, a ZnS layer and a YbF layer₃Layer, MgF₂Layer of Al₂O₃Layer, SiO₂Coating a film layer structure on the surface of the substrate layer and simultaneously adopting a Kaufman ion source assisted deposition mode;

step S2, SiO film structure is deposited without using Kaufman ion source to assist deposition₂The surface of the layer is plated with a waterproof layer.

8. The method for manufacturing the antireflection film with high optical performance and strong environmental adaptability suitable for the wavelength band of 3.7 to 4.8 μm according to claim 7, wherein the plating temperature is controlled to 130 to 150 ℃ in step S1.

9. The method for manufacturing the antireflection film with high optical performance and strong environmental adaptability suitable for the wavelength band of 3.7 to 4.8 μm according to claim 7, wherein in step S1, the control parameters in the koffman ion source assisted deposition mode are as follows: the filling gas is argon, the gas flow is 8-15 sccm, the anode voltage is 45-55V, the cathode voltage is 8-10V, the cathode current is 10-15A, the beam current is 100mA, the screen electrode voltage is 300-400V, and the bias current is 100-120 mA.

10. The method for manufacturing the antireflection film with high optical performance and strong environmental adaptability suitable for the wavelength band of 3.7 to 4.8 μm according to claim 7, wherein the plating temperature is controlled to be 25 to 35 ℃ in step S2.

Technical Field

The invention relates to the technical field of infrared coating, in particular to a high-optical-performance strong-environmental-adaptability anti-reflection film applicable to a 3.7-4.8 mu m waveband and a preparation method thereof.

Background

In an infrared optical system, most infrared optical elements need to be plated with an antireflection film to reduce the surface reflection loss, the service life of the optical elements in a severe environment is prolonged through plating, and the stability of the performance of an optical machine of the system is kept. With the development of modern optical instrument equipment, the requirement on the infrared antireflection film is higher and higher, the residual reflection of the film layer is required to be reduced, the film layer is required to bear harsher environmental conditions, and particularly, the higher requirement on the wear resistance of the antireflection film is provided. The existing anti-reflection film with the wave band of 3.7-4.8 mu m has the following film layer structure: basal layer | Ge ZnSGe ZnS YbF₃ZnS | air has the average transmittance of 98.0% in a wave band of 3.7-4.8 mu m and the average reflectance of 0.6%, cannot bear the moderate friction test in the GJB2485-1995 standard, cannot well meet the use requirement of a novel optical instrument, and limits the development of high-quality infrared optical elements.

Disclosure of Invention

The invention aims to provide a high-optical-performance strong-environmental-adaptability antireflection film suitable for a 3.7-4.8 mu m waveband and a preparation method thereof, and aims to solve the technical problems that in the prior art, the 3.7-4.8 mu m waveband antireflection film is poor in optical performance and environmental adaptability and cannot well meet the use requirements of a novel optical instrument.

In order to achieve the purpose, the invention provides the following technical scheme:

the anti-reflection film with high optical performance and strong environmental adaptability and suitable for the wave band of 3.7-4.8 mu m comprises a substrate layer, an air layer and a film layer structure arranged between the substrate layer and the air layer from bottom to top; the base layer is made of one of Ge, Si, ZnS and ZnSe; the film structure is a multilayer film, and the Ge layer, the ZnS layer, the Ge layer, the ZnS layer and the YbF are sequentially connected from bottom to top₃Layer, MgF₂Layer of Al₂O₃Layer, SiO₂Layer, waterproof layer. The film structure not only meets the requirement of a film structure with high and low refractive index materials alternately, but also realizes the improvement of the transmittance of a specific wave band of 3.7-4.8 mu m, and MgF is adopted₂Layer of Al₂O₃Layer, SiO₂The structure of the layer and the waterproof layer ensures the salt solution soaking resistance and the friction resistance of the film layer. Wherein the MgF2 layer functions as a ZnS layer and Al₂O₃Connection layers between layers, Al₂O₃The layer serves to increase the mechanical strength of the surface of the film, SiO₂The layer functions as Al₂O₃The waterproof layer is used for protecting the film layer from being corroded by corrosive liquid such as salt solution.

The thickness of each layer of the film layer structure is adjusted according to the material of the substrate layer.

When the substrate layer is made of Ge material, the thickness of each layer of film layer of the film layer structure is as follows in sequence: 31.53nm Ge layer, 183.15nm ZnS layer, 59.89nm Ge layer, 94.17nm ZnS layer, 545.00nm YbF3 layer and MgF₂Layer of 50.00nm, Al₂O₃The layer is 90.00nm, SiO₂The layer is 20.00nm and the waterproof layer is 10 nm.

When the base layer is made of Si material, the thickness of each layer of the film layer structure is as follows: 98.12nm Ge layer, 207.68nm ZnS layer, 54.01nm Ge layer, 168.58nm ZnS layer and YbF₃The layer is 505.00nm,MgF₂Layer of 50.00nm, Al₂O₃The layer is 90.00nm, SiO₂The layer is 20nm and the waterproof layer is 10 nm.

When the base layer is made of ZnS material, the thickness of each layer of the film layer structure is as follows: 31.32nm Ge layer, 321.34nm ZnS layer, 30.79nm Ge layer, 352.48nm ZnS layer, YbF₃The layer is 468.00nm MgF₂Layer of 50.00nm, Al₂O₃The layer is 90.00nm, SiO₂The layer is 20nm and the waterproof layer is 10 nm.

When the base layer is made of ZnSe material, the thickness of each layer of the film layer structure is as follows: a Ge layer of 37.55nm, a ZnS layer of 300.97nm, a Ge layer of 363.22nm, a ZnS layer of 498.00nm, YbF₃The layer is 498.00nm MgF₂Layer of 50.00nm, Al₂O₃The layer is 90.00nm, SiO₂The layer is 20nm and the waterproof layer is 10 nm.

The preparation method of the anti-reflection film with high optical performance and strong environmental adaptability and suitable for the wave band of 3.7-4.8 mu m comprises the following steps:

step S1, plating a film layer structure on the surface of the substrate layer, and sequentially plating a Ge layer, a ZnS layer, a Ge layer, a ZnS layer and YbF₃Layer, MgF₂Layer of Al₂O₃Layer, SiO₂A layer; two of which are Ge layers, MgF₂Layer of Al₂O₃Layer, SiO₂The layer is plated by adopting an electron beam heating evaporation mode, and the evaporation rate of electron beam heating is controlled to be 0.4-0.6 nm/s; two ZnS layers, YbF₃The layer is plated in a resistance heating evaporation mode, and the evaporation rate of resistance heating is controlled to be 1-2 nm/s; and plating a film layer structure on the surface of the substrate layer and simultaneously adopting a Kaufman ion source assisted deposition mode;

step S2, adopting resistance heating evaporation mode to form SiO film layer structure₂The surface of the layer is plated with a waterproof layer, and the koffman ion source is not used for assisting deposition.

Further, in step S1, the plating temperature is controlled to 130-150 ℃.

Further, in step S1, the control parameters in the koffman ion source assisted deposition method are: the filling gas is argon, the gas flow is 8-15 sccm, the anode voltage is 45-55V, the cathode voltage is 8-10V, the cathode current is kept at 10-15A, the beam current is 100mA, the screen electrode voltage is 300-400V, and the bias current is 100-120 mA.

Further, in step S2, the plating temperature is controlled to be 25 to 35 ℃.

Compared with the prior art, the anti-reflection film with high optical performance and strong environmental adaptability and the preparation method thereof, which are suitable for the wave band of 3.7-4.8 μm, has the following beneficial effects:

the anti-reflection film with high optical performance and strong environmental adaptability and suitable for the wave band of 3.7-4.8 mu m and the preparation method thereof in the invention design the MgF layer on the basis of a film stack with four Ge layers, ZnS layers, Ge layers and ZnS layers₂Layer of Al₂O₃Layer, SiO₂The reinforced film stack composed of the layer and the waterproof layer not only realizes that the transmittance of the anti-reflection film is more than or equal to 99% in the wave band of 3.7-4.8 μm and the reflectivity is less than or equal to 0.3%, but also enhances the environmental adaptability of the anti-reflection film, so that the film layer has higher salt solution corrosion resistance and friction resistance compared with the original anti-reflection film. The method specifically comprises the following steps: the film layer can be soaked in a NaCl solution with the mass ratio of 5 +/-1% and the PH value of 6.5-7.2 for 1 year, the film layer is not damaged, and the original anti-corrosion film can generate corrosion points after being soaked in a saline solution for 24 hours; the clean and dry absorbent cotton yarn cloth is overlapped into 6 layers to be wrapped on the rubber, a friction test of 4.9N back and forth 100 times (50 back and forth) is carried out on the surface of the film layer, the film layer has no scratch, and the original anti-reflection film can have the scratch after friction. In practical application, the imaging quality of an optical instrument can be effectively improved, and the service life of the equipment in a severe environment can be effectively prolonged.

Drawings

In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.

FIG. 1 is a cross-sectional view of a high optical performance environmentally friendly antireflective film of the present invention for use in the wavelength range of 3.7-4.8 μm;

FIG. 2 is a graph of transmittance spectra of a high optical quality environmentally friendly antireflective film prepared in example 2 of the present invention;

FIG. 3 is a reflectance spectrum plot of a high optical quality environmentally compatible antireflective film prepared in example 2 of the invention.

Detailed Description

The technical solutions of the present invention will be described clearly and completely with reference to the accompanying drawings, and it is to be understood that the described embodiments are only a part of the embodiments of the present invention, and 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.

Example 1

As shown in FIG. 1, the anti-reflection film with high optical performance and strong environmental adaptability, which is suitable for the wavelength band of 3.7-4.8 μm, of the present invention includes 11 film layers including a substrate layer and an air layer, the substrate layer may be one of Ge, Si, ZnS or ZnSe materials, and the film layer structure is a Ge layer, a ZnS layer, a YbF layer, which are connected in sequence from bottom to top₃Layer, MgF₂Layer of Al₂O₃Layer, SiO₂Layer, waterproof layer.

Sequentially plating a Ge layer, a ZnS layer, a Ge layer, a ZnS layer and YbF on the surface of the substrate layer₃Layer, MgF₂Layer of Al₂O₃Layer and SiO₂In the process of the layer, the plating temperature is controlled at 130 ℃, meanwhile, a Kaufman ion source is adopted for auxiliary deposition, the gas filled is argon, the gas flow is 12sccm, the anode voltage is 50V, the cathode voltage is 10V, the cathode current is kept at 15A, the beam current is 100mA, the screen electrode voltage is 300V, and the bias current is 120 mA; plating a 10nm waterproof layer at 27 ℃ under the ion source-free auxiliary condition; the anti-reflection film with high optical performance and strong environmental adaptability, which is suitable for the wave band of 3.7-4.8 mu m, is obtained.

And measuring the transmittance of the antireflection film with high optical performance and strong environmental adaptability, and measuring that the average transmittance of the antireflection film is 99.11%.

And measuring the reflectivity of the antireflection film with high optical performance and strong environmental adaptability, and measuring that the average reflectivity of the antireflection film is 0.3%.

The part is placed into NaCl solution with the mass ratio of 5% and the PH value of 7.1 and soaked for 30 days, and the surface of the film layer is not corroded. The 6-layer degreased cotton gauze rubber is wrapped on the surface of the film layer, and a friction test of 4.9N back and forth 100 times (50 back and forth) is carried out on the surface of the film layer, so that the film layer has no scratch.

Example 2

Selecting planar Ge material part of phi 35mm × 2mm, plating film layer structure on the surface layer of one surface of the substrate within the wavelength range of 3.7-4.8 μm, and sequentially plating 31.53nm Ge, 183.15nm ZnS, 59.89nm Ge, 94.17nm ZnS, 545.00nm YbF3 and 50.00nm MgF at 135 deg.C₂、90.00nm Al₂O₃、20.00nm SiO₂Meanwhile, a Kaufman ion source assisted deposition mode is adopted, the flow of argon gas is filled to be 9sccm, the anode voltage is 50V, the cathode voltage is 10V, the cathode current is kept at 15A, the beam current is 100mA, the screen electrode voltage is 310V, and the bias current is 120 mA; plating a 10nm waterproof layer at 26 ℃ under the auxiliary condition of no ion source; the anti-reflection film with high optical performance and strong environmental adaptability, which is suitable for the wave band of 3.7-4.8 mu m, is obtained.

As shown in fig. 2, when transmittance measurement was performed on the antireflection film with high optical performance and strong environmental suitability, the average transmittance of the antireflection film was measured to be 99.15%.

As shown in fig. 3, when the reflectance of the antireflective film with high optical performance and strong environmental adaptability was measured, the average reflectance of the antireflective film was measured to be 0.29%.

The part is placed into NaCl solution with the mass ratio of 5% and the PH value of 7.1, and is soaked for 1 year, and the surface of the film layer is not corroded. The 6-layer degreased cotton gauze rubber is wrapped on the surface of the film layer, and a friction test of 4.9N back and forth 100 times (50 back and forth) is carried out on the surface of the film layer, so that the film layer has no scratch.

Example 3

Selecting planar ZnSe material parts with phi of 25.4mm multiplied by 3mm, plating a film layer structure on the surface layer of one surface of the substrate within the range of 3.7-4.8 mu m of wave band, and sequentially plating 37.55nm Ge, 300.97nm ZnS, 31.31nm Ge, 363.22nm ZnS and 498.00nm YbF at 140 DEG C₃、50.00nm MgF₂、90.00nm Al₂O₃、20.00nm SiO₂Meanwhile, a Kaufman ion source auxiliary deposition mode is adopted, argon gas is filled into the reactor, the flow rate is 15sccm, the anode voltage is 50V, the cathode voltage is 10V, the cathode current is kept at 15A, the beam current is 100mA, the screen electrode voltage is 300V, and the bias current is 100 mA; plating a 10nm waterproof layer at 25 ℃ under the ion source-free auxiliary condition; the anti-reflection film with high optical performance and strong environmental adaptability, which is suitable for the wave band of 3.7-4.8 mu m, is obtained.

And measuring the transmittance of the antireflection film with high optical performance and strong environmental adaptability, and measuring that the average transmittance of the antireflection film is 99.10%.

And measuring the reflectivity of the antireflection film with high optical performance and strong environmental adaptability, and measuring that the average reflectivity of the antireflection film is 0.3%.

The part is placed into NaCl solution with the mass ratio of 5% and the PH value of 7.1 and soaked for 30 days, and the surface of the film layer is not corroded. The 6-layer degreased cotton gauze rubber is wrapped on the surface of the film layer, and a friction test of 4.9N back and forth 100 times (50 back and forth) is carried out on the surface of the film layer, so that the film layer has no scratch.

Example 4

Selecting planar Si material parts of phi 100mm multiplied by 5mm, plating a film layer structure on the surface layer of one surface of a substrate within the range of 3.7-4.8 mu m of wave band, and sequentially plating 98.12nm Ge, 207.68nm ZnS, 54.01nm Ge, 168.58nm ZnS and 505.00nm YbF at 135 DEG C₃、50.00nm MgF₂、90.00nm Al₂O₃20nm SiO2, and simultaneously adopting a Kaufman ion source assisted deposition mode, charging argon gas with the flow rate of 14sccm, the anode voltage of 55V, the cathode voltage of 10V, the cathode current of 15A, the beam current of 100mA, the screen electrode voltage of 350V and the bias current of 120 mA; and plating a 10nm waterproof layer at 30 ℃ under the ion source-free auxiliary condition to obtain the high-optical-performance strong-environmental-adaptability anti-reflection film applicable to the wave band of 3.7-4.8 microns.

And measuring the transmittance of the antireflection film with high optical performance and strong environmental adaptability, and measuring that the average transmittance of the antireflection film is 99.23%.

And measuring the reflectivity of the antireflection film with high optical performance and strong environmental adaptability, and measuring that the average reflectivity of the antireflection film is 0.27%.

The part is placed into NaCl solution with the mass ratio of 5% and the PH value of 7.1, and is soaked for 180 days, and the surface of the film layer is not corroded. The 6-layer degreased cotton gauze rubber is wrapped on the surface of the film layer, and a friction test of 4.9N back and forth 100 times (50 back and forth) is carried out on the surface of the film layer, so that the film layer has no scratch.

Example 5

Selecting ZnS lens with phi of 50mm, plating a film structure on the surface layer of one surface of the substrate within the range of 3.7-4.8 μm of wavelength band, and sequentially plating 31.32nm Ge, 321.34nm ZnS, 30.79nm Ge, 352.48nm ZnS and 468.00nm YbF at 135 DEG C₃、50.00nm MgF₂、90.00nm Al₂O₃And 20.00nm of SiO2, and simultaneously adopting a Kaufman ion source assisted deposition mode, filling argon gas with the flow rate of 12sccm, the anode voltage of 47V, the cathode voltage of 10V, the cathode current of 12A, the beam current of 100mA, the screen electrode voltage of 370V and the bias current of 120mA, and plating a 10nm waterproof layer at 35 ℃ under the condition of no ion source assistance to obtain the high-optical-performance strong-environment-adaptability antireflection film applicable to the 3.7-4.8 mu m waveband.

And measuring the transmittance of the antireflection film with high optical performance and strong environmental adaptability, and measuring that the average transmittance of the antireflection film is 99.09%.

And measuring the reflectivity of the antireflection film with high optical performance and strong environmental adaptability, and measuring that the average reflectivity of the antireflection film is 0.29%.

The part is placed into NaCl solution with the mass ratio of 5% and the PH value of 7.1, and is soaked for 180 days, and the surface of the film layer is not corroded. The 6-layer degreased cotton gauze rubber is wrapped on the surface of the film layer, and a friction test of 4.9N back and forth 100 times (50 back and forth) is carried out on the surface of the film layer, so that the film layer has no scratch.

The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention, and all the changes or substitutions should be covered within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.