阅读说明：本技术 一种ZnSe基底7.7-9.5μm波段高耐用性减反膜及制备方法 (ZnSe substrate 7.7-9.5 mu m waveband high-durability antireflection film and preparation method thereof ) 是由 李刚 董力 张友良 杨伟声 张红梅 吴栋才 耿曙 王宇彤 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,具体涉及一种ZnSe基底7.7-9.5μm波段高耐用性减反膜及制备方法,其中ZnSe基底7.7-9.5μm波段高耐用性减反膜,为设置在基层表面并与空气接触的膜层结构,并由依次叠层连接的ZnSe层、Ge层、ZnSe层、Ge层、ZnSe层、YbF3层、ZnS层构成。本发明的ZnSe基底7.7-9.5μm波段高耐用性减反膜,用于为解决现有技术中,ZnSe材料基底7.7-9.5μm波段减反膜光学性能不佳,抗盐溶液浸泡和抗摩擦能力不强,无法很好地满足新型光学仪器的使用要求的技术问题。(The invention relates to the technical field of infrared coating, in particular to a 7.7-9.5 mu m waveband high-durability antireflection film of a ZnSe substrate and a preparation method thereof, wherein the 7.7-9.5 mu m waveband high-durability antireflection film of the ZnSe substrate is a film structure which is arranged on the surface of a base layer and is in contact with air, and consists of a ZnSe layer, a Ge layer, a ZnSe layer, a YbF3 layer and a ZnS layer which are sequentially connected in a laminated manner. The invention relates to a 7.7-9.5 mu m waveband high-durability antireflection film of a ZnSe substrate, which is used for solving the technical problems that in the prior art, the 7.7-9.5 mu m waveband antireflection film of the ZnSe material substrate has poor optical performance, and has weak salt solution soaking and friction resistance, so that the using requirements of a novel optical instrument cannot be well met.)

1. A ZnSe substrate anti-reflection film with high durability and 7.7-9.5 μm wave band is a film structure which is arranged on the surface of a base layer and is in contact with air, and is characterized in that: the film layer structure is composed of a ZnSe layer, a Ge layer, a ZnSe layer, a YbF3 layer and a ZnS layer which are sequentially connected in a laminated mode.

2. A method for preparing a 7.7-9.5 μm band high durability antireflection film of a ZnSe substrate as defined in claim 1, characterized by comprising the steps of:

step S1, bombarding the surface of the substrate by using an APS ion source of physical vapor deposition coating equipment for 6 min;

step S2, using physical vapor deposition coating equipment and adopting an APS ion source assisted deposition mode to sequentially coat a ZnSe layer with the thickness of 50nm, a Ge layer with the thickness of 122.05nm, a ZnSe layer with the thickness of 679.67nm, a Ge layer with the thickness of 154.76nm, a ZnSe layer with the thickness of 230.54nm, a YbF3 layer with the thickness of 840.00nm and a ZnS layer with the thickness of 255nm on the surface of the base layer;

and step S3, using plasma chemical vapor deposition coating equipment, and performing plasma bombardment on the film layer by using an RF (radio frequency) source for 20 min.

3. The method for preparing a 7.7-9.5 μm waveband high-durability antireflection film of a ZnSe substrate according to claim 2, wherein: in step S1, the control parameters for APS ion source bombardment are: the gas is argon, the gas flow is 8-10sccm, the bias voltage is 120-.

4. The method for preparing a 7.7-9.5 μm waveband high-durability antireflection film of a ZnSe substrate according to claim 2, wherein: in step S2, the plating temperature is controlled at 130-150 ℃.

5. The method for preparing a 7.7-9.5 μm waveband high-durability antireflection film of a ZnSe substrate according to claim 2, wherein: in step S2, the control parameters in the APS ion source assisted deposition method are: the gas is argon, the gas flow is 8-10sccm, the bias voltage is 120-.

6. The method for preparing a ZnSe substrate having a waveband of 7.7 to 9.5 μm and a high durability antireflection film according to claim 2, wherein in the step S3, the control parameters of the RF source bombardment of the plasma CVD coating equipment are as follows: the filling gas is argon, the gas flow is 100-.

Technical Field

The invention relates to the technical field of infrared coating, in particular to a 7.7-9.5 mu m waveband high-durability antireflection film of a ZnSe substrate and a preparation method thereof.

Background

ZnSe is widely used in infrared optical systems as a material having good optical transmittance in the infrared band. With the continuous development of infrared optical instruments, the requirements on the imaging quality of optical systems are higher and higher. The traditional ZnSe material substrate is a 7.7-9.5 mu m waveband antireflection film, the average transmittance in a waveband is about 98%, and a film layer cannot bear the examination of salt solution soaking and moderate friction in the GJB2485-1995 standard and cannot meet the use requirement of a latest infrared optical system.

Disclosure of Invention

The invention provides a 7.7-9.5 mu m waveband high-durability antireflection film of a ZnSe substrate and a preparation method thereof, which are used for solving the technical problems that in the prior art, the 7.7-9.5 mu m waveband antireflection film of the ZnSe substrate has poor optical performance, and has weak salt solution soaking and friction resistance, so that the application requirements of a novel optical instrument cannot be well met.

In order to achieve the purpose, the invention provides the following technical scheme: the anti-reflection film with the high durability and the 7.7-9.5 mu m waveband for the ZnSe substrate is a film layer structure which is arranged on the surface of a base layer and is in contact with air, wherein the film layer is formed by sequentially laminating and connecting a ZnSe layer, a Ge layer, a ZnSe layer, a YbF3 layer and a ZnS layer.

Preferably, the preparation method of the ZnSe substrate anti-reflection film with high durability in a waveband of 7.7 to 9.5 mu m comprises the following steps:

step S1, bombarding the surface of the substrate by using an APS ion source of physical vapor deposition coating equipment for 6 min;

step S2, using physical vapor deposition coating equipment and adopting an APS ion source assisted deposition mode to sequentially coat a ZnSe layer with the thickness of 50nm, a Ge layer with the thickness of 122.05nm, a ZnSe layer with the thickness of 679.67nm, a Ge layer with the thickness of 154.76nm, a ZnSe layer with the thickness of 230.54nm, a YbF3 layer with the thickness of 840.00nm and a ZnS layer with the thickness of 255nm on the surface of the base layer;

and step S3, using plasma chemical vapor deposition coating equipment, and performing plasma bombardment on the film layer by using an RF (radio frequency) source for 20 min.

Preferably, in step S1, the control parameters of the APS ion source bombardment are: the gas is argon, the gas flow is 8-10sccm, the bias voltage is 120-.

Preferably, in step S2, the plating temperature is controlled at 130-150 ℃.

Preferably, in step S2, the control parameters in the APS ion source assisted deposition method are: the gas is argon, the gas flow is 8-10sccm, the bias voltage is 120-.

Preferably, in step S3, the control parameters of the RF source bombardment of the plasma chemical vapor deposition coating apparatus are: the filling gas is argon, the gas flow is 100-.

The invention has the beneficial effects that: the high-durability antireflection film with the waveband of 7.7-9.5 mu m of the ZnSe substrate takes ZnSe material as the substrate and designs the structure as follows: the film system structure comprises a ZnSe layer with the thickness of 50nm, a Ge layer with the thickness of 122.05nm, a ZnSe layer with the thickness of 679.67nm, a Ge layer with the thickness of 154.76nm, a ZnSe layer with the thickness of 230.54nm, a YbF3 layer with the thickness of 840.00nm and a ZnS layer with the thickness of 255nm, and the structure effectively improves the transmittance of the antireflection film. In addition, in the preparation process, the compactness and the mechanical strength of the film layer on the surface of the anti-reflection film are enhanced by carrying out plasma bombardment on the film layer, and the salt solution corrosion resistance and the friction resistance of the anti-reflection film are improved.

Compared with the prior art: the film layer can be soaked in NaCl solution with the mass ratio of 5 +/-1% and the PH value of 6.5-7.2 for 30 days (the detection standard of 3.4.3.2 salt solubility in GJB2585-1995 (general Specification for optical film layer) is soaking for 24 hours), and the film layer is not damaged; a clean and dry cotton wool gauze was laid in 6 layers and wrapped on a rubber, and a rubbing test was performed on the surface of the film layer 100 times (50 times) at 4.9N back and forth (50 back and forth) with no scratch on the film layer, according to the test standard of 3.4.1.3 moderate rubs in GJB2585-1995 "general Specification for optical film layers". 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 schematic cross-sectional view of a 7.7-9.5 μm band highly durable antireflective film of a ZnSe substrate in accordance with the present invention;

FIG. 2 is a graph of the transmittance spectrum of a 7.7-9.5 μm band high durability antireflective film of a ZnSe substrate prepared in example 4 of the present invention;

FIG. 3 is a graph of reflectance spectra of 7.7-9.5 μm band high durability antireflective films of ZnSe substrates prepared in example 4 of the present 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.

As shown in figure 1, the anti-reflection film with high durability in a 7.7-9.5 mu m waveband of the ZnSe substrate is a film layer structure which is arranged on the surface of a base layer and is in contact with air, wherein the film layer is formed by sequentially laminating and connecting a ZnSe layer, a Ge layer, a ZnSe layer, a YbF3 layer and a ZnS layer. Before plating, a 7.7-9.5 mu m waveband high-durability antireflection film on a ZnSe substrate is bombarded on the surface of the substrate for 6min by using an APS ion source of physical vapor deposition coating equipment, wherein the gas is filled into the substrate to be argon, the gas flow is 8-10sccm, the bias voltage is 120-130V, the discharge voltage is 60-90V, the discharge current is kept at 20-40A, and the coil current is 1-4A;

in the process of sequentially plating a ZnSe layer, a Ge layer, a ZnSe layer, a YbF3 layer and a ZnS layer on the surface of the substrate layer, the plating temperature is controlled at 130-;

after plating, an RF radio frequency source of a plasma chemical vapor deposition coating device is used for carrying out plasma bombardment on the film layer, the bombardment time is 20min, the gas is argon, the gas flow is 100-.

Example 1

Selecting a ZnSe material lens with phi of 37.5mm, bombarding the surface layer of one surface of the substrate in a range with a wave band of 7.7-9.5 microns for 6min by adopting an APS ion source and filling argon, wherein the gas flow is 10sccm, the bias voltage is 120V, the discharge voltage is 80V, the discharge current is 30A, and the coil current is 2A; under 140 ℃, adopting an APS ion source auxiliary deposition mode, filling argon, plating a ZnSe layer with the thickness of 50nm, a Ge layer with the thickness of 122.05nm, a ZnSe layer with the thickness of 679.67nm, a Ge layer with the thickness of 154.76nm, a ZnSe layer with the thickness of 230.54nm, a YbF3 layer with the thickness of 840.00nm and a ZnS layer with the thickness of 255nm in sequence, wherein the gas flow is 10sccm, the bias voltage is 120V, the discharge voltage is 80V, the discharge current is 35A and the coil current is 2A; and (3) filling argon into an RF (radio frequency) source of plasma chemical vapor deposition coating equipment, wherein the gas flow is 150sccm, the power is 400W, and performing plasma bombardment on the film layer for 20 min. The applicable ZnSe substrate of the invention with high durability at the waveband of 7.7-9.5 mu m is obtained.

The transmittance of the high-durability antireflection film with the waveband of 7.7-9.5 mu m of the ZnSe substrate was measured, and the average transmittance of the antireflection film was measured to be 99.09%.

Reflectance measurements were performed on the 7.7-9.5 μm waveband high durability antireflective film of the ZnSe substrate, and the average reflectance of the antireflective film was found to be 0.3%.

The part is placed into NaCl solution with the mass ratio of 5% and the PH value of 7.1, and is soaked for 24 hours, 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 is carried out on the surface of the film layer for 100 times at 4.9N back and forth, so that the film layer has no scratch.

Example 2

Selecting a planar ZnSe material part with phi of 26mm multiplied by 2mm, carrying out bombardment on the surface layer of one surface of the substrate within the range of 7.7-9.5 microns of wave band by adopting an APS ion source, introducing argon gas, wherein the gas flow is 9sccm, the bias voltage is 125V, the discharge voltage is 90V, the discharge current is 40A, the coil current is 4A, and the bombardment time is 6 min; under 130 ℃, adopting an APS ion source auxiliary deposition mode, filling argon, wherein the gas flow is 9sccm, the bias voltage is 125V, the discharge voltage is 90V, the discharge current is 40A, and the coil current is 4A, and sequentially plating a ZnSe layer with the thickness of 50nm, a Ge layer with the thickness of 122.05nm, a ZnSe layer with the thickness of 679.67nm, a Ge layer with the thickness of 154.76nm, a ZnSe layer with the thickness of 230.54nm, a YbF3 layer with the thickness of 840.00nm and a ZnS layer with the thickness of 255 nm; and (3) filling argon into an RF (radio frequency) source of plasma chemical vapor deposition coating equipment, wherein the gas flow is 200sccm, the power is 500W, and performing plasma bombardment on the film layer for 20 min. The applicable ZnSe substrate of the invention with high durability at the waveband of 7.7-9.5 mu m is obtained.

The transmittance of the high-durability antireflection film with the waveband of 7.7-9.5 mu m of the ZnSe substrate is measured, and the average transmittance of the antireflection film is 99.10 percent.

Reflectance measurements were performed on the 7.7-9.5 μm waveband high durability antireflective film of the ZnSe substrate, and the average reflectance of the antireflective film was found to be 0.3%.

The part is placed into NaCl solution with the mass ratio of 5% and the PH value of 7.1, and is soaked for 48 hours, 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 is carried out on the surface of the film layer for 100 times at 4.9N back and forth, so that the film layer has no scratch.

Example 3

Selecting planar ZnSe material parts with phi of 40mm multiplied by 3mm, carrying out bombardment on the surface layer of one surface of the substrate within the range of 7.7-9.5 microns of wave band by adopting an APS ion source, introducing argon gas, wherein the gas flow is 8sccm, the bias voltage is 120V, the discharge voltage is 70V, the discharge current is 25A, the coil current is 2A, and the bombardment time is 6 min; under 150 ℃, adopting an APS ion source auxiliary deposition mode, filling argon, plating a ZnSe layer with the thickness of 50nm, a Ge layer with the thickness of 122.05nm, a ZnSe layer with the thickness of 679.67nm, a Ge layer with the thickness of 154.76nm, a ZnSe layer with the thickness of 230.54nm, a YbF3 layer with the thickness of 840.00nm and a ZnS layer with the thickness of 255nm in sequence, wherein the gas flow is 10sccm, the bias voltage is 120V, the discharge voltage is 70V, the discharge current is 30A and the coil current is 2A; and (3) filling argon into an RF (radio frequency) source of plasma chemical vapor deposition coating equipment, wherein the gas flow is 100sccm, the power is 400W, and performing plasma bombardment on the film layer for 20 min. The applicable ZnSe substrate of the invention with high durability at the waveband of 7.7-9.5 mu m is obtained.

The transmittance of the high-durability antireflection film with the waveband of 7.7-9.5 mu m of the ZnSe substrate is measured, and the average transmittance of the antireflection film is 99.10 percent.

Reflectance measurements were performed on the 7.7-9.5 μm waveband high durability antireflective film of the ZnSe substrate, and 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 48 hours, 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 is carried out on the surface of the film layer for 100 times at 4.9N back and forth, so that the film layer has no scratch.

Example 4

Selecting a planar ZnSe material part with phi of 25.4mm multiplied by 2mm, adopting an APS ion source to charge argon in the surface layer of one surface of the substrate within the range of 7.7-9.5 mu m of wave band, introducing the argon, charging the gas with the gas flow of 10sccm, bias voltage of 125V, discharge voltage of 80V, discharge current of 30A, coil current of 3A, and bombarding for 6 min; under 145 ℃, adopting an APS ion source auxiliary deposition mode, filling argon, plating a ZnSe layer with the thickness of 50nm, a Ge layer with the thickness of 122.05nm, a ZnSe layer with the thickness of 679.67nm, a Ge layer with the thickness of 154.76nm, a ZnSe layer with the thickness of 230.54nm, a YbF3 layer with the thickness of 840.00nm and a ZnS layer with the thickness of 255nm in sequence, wherein the gas flow is 10sccm, the bias voltage is 125V, the discharge voltage is 80V, the discharge current is 35A and the coil current is 3A; and (3) filling argon into an RF (radio frequency) source of plasma chemical vapor deposition coating equipment, wherein the gas flow is 200sccm, the power is 600W, and performing plasma bombardment on the film layer for 20 min. The applicable ZnSe substrate of the invention with high durability at the waveband of 7.7-9.5 mu m is obtained.

Transmittance measurements were made on the 7.7-9.5 μm waveband high durability antireflective film of the ZnSe substrate, and the average transmittance of the antireflective film was measured to be 99.11%, as shown in fig. 2.

Reflectance measurements were performed on the 7.7-9.5 μm waveband high durability antireflective film of the ZnSe substrate, and the average reflectance of the antireflective film was measured to be 0.29%, as shown in fig. 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 is carried out on the surface of the film layer for 100 times at 4.9N back and forth, 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.