CN115576038A - High-transmittance 9.2-10.7-micrometer laser broadband antireflection film and preparation method thereof - Google Patents
High-transmittance 9.2-10.7-micrometer laser broadband antireflection film and preparation method thereof Download PDFInfo
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- CN115576038A CN115576038A CN202211121810.3A CN202211121810A CN115576038A CN 115576038 A CN115576038 A CN 115576038A CN 202211121810 A CN202211121810 A CN 202211121810A CN 115576038 A CN115576038 A CN 115576038A
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Abstract
The invention discloses a laser broadband antireflection film with high transmittance of 9.2-10.7 mu m and a preparation method thereof, wherein the laser broadband antireflection film with high transmittance of 9.2-10.7 mu m has a film system structure as follows: SUB/k 1 Lk 2 H 1 k 3 Lk 4 H 2 /AIR, wherein SUB represents a zinc selenide substrate, AIR represents AIR, H1 represents a zinc selenide layer, H2 represents a zinc sulfide layer, L represents a YB layer, and the YB layer is an aluminum-doped YF 3 With calcium-doped BaF 3 A mixed film layer with the volume ratio of (2-3) to 1, k 1 ‑k 4 A coefficient representing a quarter reference wavelength optical thickness of each layer. The high-transmittance 9.2-10.7 mu m laser broadband antireflection film has the advantages that the average single-side reflectivity is not more than 0.08%, the average double-side transmittance is not less than 99.78%, the film stress is basically eliminated through the selection and the matching of film materials, the adhesive force of the film is improved, the obtained film has strong wear resistance and good high and low temperature resistance.
Description
Technical Field
The invention relates to a laser broadband antireflection film with high transmittance of 9.2-10.7 microns and a preparation method thereof, belonging to the technical field of laser broadband high-efficiency antireflection films.
Background
In an optical element, light energy is lost due to reflection on the surface of the element, and in order to reduce the reflection loss on the surface of the element, a transparent dielectric film is often coated on the surface of the optical element, and such a film is called an antireflection film.
In the preparation process of the antireflection film, the optical properties such as reflectivity and transmissivity of the corresponding wave band need to be considered, and the mechanical properties such as film stress and adhesive force need to be considered, so that the use requirement can be better met. The film layer stress can directly cause the phenomena of film falling, color cracking and the like, and the performance of the product in all aspects is seriously influenced, so that the film layer stress is reduced or even eliminated, and the preparation of the antireflection film is very important. The reflectivity and the transmissivity are very important parameters for evaluating the performance of the antireflection film, and due to the importance of the antireflection film to an optical element, a plurality of research and development personnel are dedicated to the development of the antireflection film, and certain achievements are achieved on the reduction of the reflectivity and the improvement of the transmissivity of the antireflection film, for example, the patent application with the application number of CN202010731907.0 discloses an antireflection film for a sapphire substrate and a preparation method thereof, wherein the transmissivity is about 97 percent, the reflectivity is about 1.5 percent, but the optical performance of the antireflection film is still required to be further improved along with the higher requirements of customers on the product quality.
Disclosure of Invention
The invention provides a laser broadband antireflection film with high transmittance of 9.2-10.7 mu m and a preparation method thereof, wherein the average single-side reflectivity is not more than 0.08%, the average double-side transmittance is not less than 99.78%, the stress of the film layer is basically eliminated, the adhesive force of the film layer is improved, and the obtained film layer has strong wear resistance and good high and low temperature resistance.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a high-transmittance 9.2-10.7 μm laser broadband antireflection film comprises: SUB/k 1 Lk 2 H 1 k 3 Lk 4 H 2 /AIR, wherein SUB represents a zinc selenide substrateAIR stands for AIR, H 1 Represents a zinc selenide layer, H 2 Represents a zinc sulfide layer, L represents a YB layer, and the YB layer is an aluminum-doped YF 3 With calcium-doped BaF 3 A mixed film layer with the volume ratio of (2-3) to 1, k 1 -k 4 A coefficient representing a quarter reference wavelength optical thickness of each layer.
The anti-reflection film basically eliminates the stress of the film layer and improves the adhesive force of the film layer through the selection and the collocation of the film layer, and the obtained film layer has strong wear resistance and good high and low temperature resistance; the average single-side reflectivity of the antireflection film is not more than 0.08%, and the average double-side transmittance is not less than 99.78%.
For the antireflection film, different wave bands and applicable substrates are different, and applicable film systems are also different; the zinc sulfide layer and the zinc selenide layer are selected, so that the scattering loss is extremely low, and the thermal shock resistance is high; by plating the YB layer, the zinc selenide layer and the zinc sulfide layer on the zinc selenide substrate according to a specific sequence, the stress problem among the film layers is effectively solved, the compactness of the film layers is improved, the film layers are firmer, the wear resistance and the temperature resistance are improved, the single-side reflectivity is reduced to be below 0.08 percent, and the double-side transmissivity is improved to be above 99.78 percent.
YF doped with aluminum in mixed film layer 3 With calcium-doped BaF 3 The selection of (1) reduces the film stress by doping aluminum and calcium in specific amounts, on the one hand, and reduces the single-sided reflectivity of the film, on the other hand.
In order to better balance the optical and mechanical properties, the aluminum-doped YF is adopted 3 In the method, the doping amount of aluminum is 2 to 6 weight percent; calcium-doped BaF 3 In the calcium content is 1wt% -20wt%.
The high-transmittance 9.2-10.7 μm wide-band anti-reflection film is double-side plated and has a film system structure of AIR/H 2 k 4 Lk 3 H 1 k 2 Lk 1 /SUB/k 1 Lk 2 H 1 k 3 Lk 4 H 2 /AIR。
K above 1 -k 4 The magnitude of (b) is related to the reference wavelength λ, k being the value at 10600nm 1 Value ofK is 0.03 to 0.06 2 Is 2.20 to 2.60, k 3 Is 0.30 to 0.60, k 4 Is 0.10-0.35.
K is the optical property and the mechanical property of the antireflection film 1 L is a first YB layer, k 2 H 1 Is a zinc selenide layer, k 3 L is a second YB layer, k 4 H 2 Is a zinc sulfide layer; the physical thickness of the first YB layer is 100 +/-20 nm, the physical thickness of the zinc selenide layer is 2680 +/-100 nm, the physical thickness of the second YB layer is 970 +/-50 nm, and the physical thickness of the zinc sulfide layer is 285 +/-20 nm.
The laser broadband antireflection film with high transmittance of 9.2-10.7 mu m is calculated by the surface type, and the film stress is close to 0. The absolute value of the calculated value less than 0.05Gpa is considered to be approximately equal to 0.
The application adopts a formula of Newton's ring method
Calculating the film stress, and when the film surface diameter ratio is more than 50 times larger than the thickness, calculating the curvature radius r of the interference seasoning to derive the film stress sigma, wherein ts is the thickness of the substrate, t f As the film thickness, es is the Young's modulus of elasticity of the substrate, and v is the Poisson's ratio of the substrate.
The ultra-low stress 9.2-10.7 mu m laser broadband antireflection film adopts ion-assisted deposition in the film coating process; before film coating, baking the zinc selenide substrate at 100-130 ℃ for 0.5-1 h; the initial vacuum degree is (0.5-0.8) × 10-3Pa during film forming, and the parameters of the ion source are as follows: the accelerating voltage is 200V, the screen electrode voltage is 450 +/-50V, and the beam current is 5-100mA.
In order to further improve the density of the deposited film and improve the optical and mechanical properties, the zinc selenide adopts a molybdenum boat evaporation-resistant mode, and the evaporation rate is controlled to be 0.3 +/-0.05 nm/s. The zinc sulfide is evaporated by adopting a copper crucible electron beam, and the evaporation rate is controlled to be 0.6 +/-0.1 nm/s.
When the YB layer is evaporated, firstly the YF doped with aluminum is evaporated 3 With calcium-doped BaF 3 Mixing according to the volume ratio of (2-3) to 1, and then adopting a molybdenum boat to prevent evaporation, wherein the evaporation rate is controlled at 0.5 +/-0.1 nm/s.
The prior art is referred to in the art for techniques not mentioned in the present invention.
The high-transmittance 9.2-10.7 mu m laser broadband antireflection film has the advantages that the average single-side reflectivity is not more than 0.08%, the average double-side transmittance is not less than 99.78%, the film stress is basically eliminated through the selection and the matching of film materials, the adhesive force of the film is improved, the obtained film has strong wear resistance and good high and low temperature resistance.
Drawings
FIG. 1 is a schematic structural view of a high transmittance 9.2-10.7 μm laser broadband antireflection film in example 1 of the present invention;
FIG. 2 is a single-sided reflection diagram of a high transmittance 9.2-10.7 μm laser broadband antireflection film design in example 1 of the present invention;
FIG. 3 is a single-sided reflection curve of the high transmittance 9.2-10.7 μm laser broadband antireflection film test in example 1 of the present invention;
FIG. 4 is a graph showing the double-sided transmission curve of the high transmittance 9.2-10.7 μm laser broadband antireflection film test in example 1 of the present invention;
FIG. 5 is a graph showing a comparison of the change of the front and rear surface types before and after single-side coating on a substrate in example 1 of the present invention (the left side is before coating and the right side is after coating);
in the figure, k 1 ～k 4 Representing the corresponding film layer.
Detailed Description
For better understanding of the present invention, the following examples are given for further illustration of the present invention, but the present invention is not limited to the following examples.
Example 1
As shown in FIG. 1, a laser broadband antireflection film with high transmittance of 9.2-10.7 μm has the following film structure: AIR/H 2 k 4 Lk 3 H 1 k 2 Lk 1 /SUB/k 1 Lk 2 H 1 k 3 Lk 4 H 2 (ii)/AIR; wherein SUB represents a zinc selenide substrate, AIR representsAir, H1 for a zinc selenide layer, H2 for a zinc sulfide layer, L for a YB layer, the YB layer being YF doped with aluminum by 5wt% 3 With 1.2 wt.% of calcium doped, k 1 Has a value of 0.04 2 Has a value of 2.30,k 3 Has a value of 0.40, k 4 Is 0.15.k is a radical of formula 1 The physical thickness of the L layer is 100nm, k 2 H 1 The physical thickness of the layer is 2680nm, k 3 The physical thickness of the L layer was 970nm, k 4 H 2 The physical thickness of the layer was 285nm.
The preparation of the laser broadband antireflection film with the high transmittance of 9.2-10.7 mu m adopts a Vietnam light 1100 type film plating machine, adopts an INFICON IC6 control instrument for crystal control, and utilizes the change of the oscillation frequency of a quartz crystal to measure the quality and the thickness of the film. The ion source adopts a Kaufman ion source developed in the nine chapters of Chinese Keke. The vacuum chamber obtains the vacuum degree required by the membrane system by the mutual matching of a mechanical pump, a diffusion pump and a deep cooling unit system, and the vacuum degree is measured by a thermocouple meter.
Performing ultrasonic cleaning on the zinc selenide substrate before film plating to remove residual dirt on the surface, baking for 1h at the baking temperature of 100 ℃, wherein the initial vacuum degree is about 7.0 x 10 during film deposition -4 Pa. The ion source parameters are set as: the accelerating voltage is 200V, the screen electrode voltage is 400V, and the beam current is about 30 mA. In the process of film deposition, a Kaufman ion source is used for assisting deposition, the concentration density is increased, and the structural integrity is improved, so that the performance and the service time of the film are improved, and the evaporation rate and the film thickness are controlled by adopting a crystal control method.
ZnSe adopts molybdenum boat to prevent evaporation heat evaporation, the evaporation rate is controlled at 0.3nm/s, znS adopts copper crucible electron beam evaporation, the evaporation rate is controlled at 0.6nm/s; when the YB layer is evaporated, firstly the YF doped with aluminum 3 With calcium-doped BaF 3 Mixing according to the volume ratio of 2.5 to 1, and then adopting a molybdenum boat to prevent evaporation, wherein the evaporation rate is controlled at 0.5nm/s.
And (3) testing results:
and (3) testing optical performance: the single-sided reflectivity and the double-sided transmittance of the film are tested by adopting an infrared spectrometer, and the obtained spectral curve meets the design requirement: the average single-sided reflectivity of 9.2-10.7 μm is less than 0.08% as shown in fig. 3-4, the average double-sided transmittance is more than 99.78%, and the film stress is calculated to be-0.02 GPa according to Newton's ring method formula by the surface type as shown in fig. 5.
Testing the performance of the film layer:
in order to ensure the reliability of the optical element, the following environmental tests are carried out on the broadband antireflection film sample according to the requirements of the general specification of the GJB2485-95 optical film layer:
(1) Abrasion resistance test: wrapping 2 layers of dry absorbent gauze outside the rubber friction head, and rubbing the film layer along the same track under the pressure of 9.8N, wherein the film layer has no damage such as scratches after 2000 times of reciprocating.
(2) Salt spray test: and (3) continuously spraying for 12h for two cycles at the ambient temperature of 35 ℃ and the NaCl concentration of 5%, wherein the total time is 24h, and the film layer is not abnormal.
(3) Soaking test: the sample was completely immersed in distilled or deionized water, and the film layer was not abnormal after one week.
(4) High and low temperature tests: keeping the temperature at minus 65 ℃ for 2 hours, quickly switching from minus 65 ℃ to 80 ℃ for 2 hours, keeping the temperature from 80 ℃ to minus 65 ℃ for 2 hours, and circulating for 12 times, wherein the film layer has no abnormality.
(5) Adhesion force experiment: the film layer is firmly adhered to the surface of the film layer by using a 3M adhesive tape with the width of 1cm, and after the adhesive tape paper is quickly pulled up from the edge of the part to the vertical direction of the surface, the film layer is not fallen or damaged, and the process is repeated for 60 times, so that the film layer is still not fallen or damaged.
Comparative example 1
Mixing YF of YB layer with aluminum 3 With calcium-doped BaF 3 Replacement is by pure YF 3 With BaF 3 Otherwise, the single-sided reflectance of the film was 0.56% in the examples 1,9.2-10.7. Mu.m, and the film stress was calculated to be-15.26 GPa.
Comparative example 2
BaF omitting calcium doping in YB layer 3 Otherwise, the single-sided reflectance of the film was 1.21% in the examples 1,9.2-10.7. Mu.m, and the film stress was calculated to be-20.35 GPa.
Comparative example 2
YF for omitting aluminum-doped YB layer 3 Otherwise, the others refer to the single-sided reflection of the embodiment 1,9.2-10.7 μmThe ratio was 1.93%, and the film stress calculation result was-22.18 GPa.
Claims (10)
1. A high-transmittance 9.2-10.7 μm laser broadband antireflection film is characterized in that: the structure of the film system is as follows: SUB/k 1 Lk 2 H 1 k 3 Lk 4 H 2 /AIR, wherein SUB represents a zinc selenide substrate, AIR represents AIR, H1 represents a zinc selenide layer, H2 represents a zinc sulfide layer, L represents a YB layer, and the YB layer is an aluminum-doped YF 3 With calcium-doped BaF 3 A mixed film layer with the volume ratio of (2-3) to 1, k 1 -k 4 A coefficient representing a quarter reference wavelength optical thickness of each layer.
2. The high transmittance 9.2-10.7 μm laser broadband antireflection film according to claim 1, characterized in that: aluminum-doped YF 3 In the content, the content of aluminum is 2wt% -6wt%.
3. The high-transmittance 9.2-10.7 μm laser broadband antireflection film according to claim 1 or 2, characterized in that: calcium-doped BaF 3 In the calcium content is 1wt% -20wt%.
4. The high-transmittance 9.2-10.7 μm laser broadband antireflection film according to claim 1 or 2, characterized in that: double-sided plating, the film system structure is AIR/H 2 k 4 Lk 3 H 1 k 2 Lk 1 /SUB/k 1 Lk 2 H 1 k 3 Lk 4 H 2 /AIR。
5. The high-transmittance 9.2-10.7 μm laser broadband antireflection film according to claim 1 or 2, characterized in that: k is a radical of 1 Is 0.03 to 0.06 2 Is 2.20 to 2.60, k 3 Is 0.30 to 0.60, k 4 The value of (A) is 0.10-0.35.
6. The high-transmittance 9.2-10.7 μm laser broadband antireflection film according to claim 1 or 2, which is characterized in thatCharacterized in that: k is a radical of 1 L is a first YB layer, k 2 H 1 Is a zinc selenide layer, k 3 L is a second YB layer, k 4 H 2 Is a zinc sulfide layer; the physical thickness of the first YB layer is 100 +/-20 nm, the physical thickness of the zinc selenide layer is 2680 +/-100 nm, the physical thickness of the second YB layer is 970 +/-50 nm, and the physical thickness of the zinc sulfide layer is 285 +/-20 nm.
7. The high-transmittance 9.2-10.7 μm laser broadband antireflection film according to claim 1 or 2, characterized in that: the average single-sided reflectivity is not more than 0.08 percent, and the average double-sided transmittance is not less than 99.78 percent.
8. The method for preparing a laser broadband antireflection film with high transmittance of 9.2 to 10.7 μm according to any one of claims 1 to 7, characterized in that: the zinc sulfide is evaporated by adopting a copper crucible electron beam, and the evaporation rate is controlled to be 0.6 +/-0.1 nm/s.
9. The method of claim 8, wherein: the zinc selenide adopts a molybdenum boat evaporation-resistant mode, and the evaporation rate is controlled to be 0.3 +/-0.05 nm/s.
10. The method of claim 8, wherein: when the YB layer is evaporated, firstly, the YF doped with aluminum is evaporated 3 With calcium-doped BaF 3 Mixing according to the volume ratio of (2-3) to 1, and then adopting a molybdenum boat to prevent evaporation, wherein the evaporation rate is controlled at 0.5 +/-0.1 nm/s.
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| CN202211121810.3A CN115576038A (en) | 2022-09-15 | 2022-09-15 | High-transmittance 9.2-10.7-micrometer laser broadband antireflection film and preparation method thereof |
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Inventor after: Liu Xiangyin Inventor after: Chen Li Inventor after: Chen Jiajia Inventor after: Li Quanmin Inventor after: Wu Yutang Inventor before: Liu Xiangyin Inventor before: Chen Li Inventor before: Chen Jiajia Inventor before: Li Quanmin Inventor before: Wu Yutang |