CN111485237A - Substrate infrared anti-reflection protective film and preparation method thereof - Google Patents
Substrate infrared anti-reflection protective film and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a substrate infrared anti-reflection protective film and a preparation method thereof, wherein the anti-reflection protective film comprises a substrate, and a first layer film, a second layer film, a third layer film and a fourth layer film which are arranged layer by layer from the surface of the substrate, wherein the first layer film and the third layer film are germanium films, the second layer film is a zinc sulfide film, and the fourth layer film is a diamond-like film; the preparation method comprises the steps of starting an ion source in a vacuum film-making environment, sequentially depositing germanium, zinc sulfide and germanium on the surface of a substrate by adopting an evaporation method in the ion-assisted vacuum film-making environment, sequentially forming a first film, a second film and a third film, and forming a fourth film on the surface of the third film by adopting a chemical vapor deposition method. The multispectral ZnS substrate infrared anti-reflection protective film and the preparation method thereof solve the problem that the film firmness, the transmittance and the higher mechanical damage resistance cannot be considered at the same time.
Description
Technical Field
The invention relates to the technical field of optical films, in particular to a substrate infrared anti-reflection protective film and a preparation method thereof.
Background
In the field of infrared optical coating, infrared optical materials are mainly used as lenses, windows and hoods of photoelectric detection systems, and are optical elements in the photoelectric detection systems, which are in direct contact with the external environment. With the upgrading and development of military equipment, the application range of the infrared optical element is wider and wider, and the infrared optical element can work at high speed or in severe environments such as wind sand, salt fog, seawater and the like for a long time, so that the requirement on the capability of resisting the severe environment of the infrared optical element is higher and higher. For example, windows or hoods in airborne, high-speed missile and ship-borne infrared imaging systems are required to be suitable for the examination of severe environment under the condition of ensuring that the optical performance is not changed.
The multispectral ZnS transmission band is 0.4-12 μm, covers the whole band from visible light to long-wave infrared and is widely applied to an infrared imaging system; the thermo-optical performance is excellent, the stability of an optical path can be kept when the ambient temperature changes, and the imaging quality is not influenced. Multispectral ZnS is therefore the first choice for the current multispectral window. However, the multispectral ZnS has a transmittance of only about 72%, and if an antireflection film is not coated, light can be reflected on an optical element for multiple times, so that illusion and halation are generated, and the imaging quality is reduced. In addition, when the multispectral ZnS is used as a detection system window or a hood, the multispectral ZnS can be impacted by solid particles such as thermal shock, free dust, hail and the like or washed by raindrops in the high-speed flight process, and the surface can seriously scatter incident light, so that the normal use of the detection system is influenced. Therefore, antireflection films and protective films must be plated on the surface of the multispectral ZnS.
The existing technology for preparing the anti-reflection protective film of the infrared window mainly comprises the following steps of 1) depositing a layer of Boron Phosphide (BP) and diamond-like carbon (D L C) film on a substrate by using a CVD method, and then depositing a layer of D L C film on the BP, wherein the film has the advantages of high adverse environment resistance, low ① transmittance and high ② cost and great harm, wherein the BP film is deposited by using two highly toxic gases of phosphane and borane, so that the environment is polluted slightly, the human body is injured seriously, and the equipment investment and maintenance cost is high.2) carbonizing germanium (Ge) filmxC1-x) The process comprises the steps of plating germanium carbide films with high refractive indexes and low refractive indexes alternately on a substrate and plating a D L C film on the outermost layer, wherein the film system has the advantages of high transmittance and good protection effect, the defects of poor process repeatability and difficulty in control of the refractive index of the ① germanium carbide film are overcome, ② is high in cost and large in harm, germane which is a highly toxic gas is needed for deposition of the germanium carbide film, environment is polluted if the germane is light, personal injury is caused if the germane is serious, and equipment investment and maintenance cost are high.
Disclosure of Invention
The invention aims to solve at least one of the problems and provides a substrate infrared anti-reflection protective film and a preparation method thereof.
According to one aspect of the invention, the substrate infrared anti-reflection protective film comprises a substrate, and a first layer of film, a second layer of film, a third layer of film and a fourth layer of film which are arranged layer by layer from the surface of the substrate, wherein the first layer of film and the third layer of film are both germanium films, the second layer of film is a zinc sulfide film, and the fourth layer of film is a diamond-like film.
Wherein the thickness of the first layer is 200-220nm, the thickness of the second layer is 480-500nm, the thickness of the third layer is 280-300nm, and the thickness of the fourth layer is 1200-1300 nm.
Wherein, the substrate is a multispectral zinc sulfide substrate.
According to another aspect of the invention, a preparation method of the substrate infrared anti-reflection protective film is provided, and the preparation method comprises the following steps: putting the substrate into a closed film-making environment; vacuumizing the film preparation environment; starting an ion source in a vacuum film-making environment; in an ion-assisted vacuum film-making environment, depositing a germanium raw material, a zinc sulfide raw material and a germanium raw material on the surface of a substrate in sequence by adopting an evaporation method, and forming a first film, a second film and a third film in sequence; turning off the ion source; and in the vacuum film-making environment without ion assistance, depositing carbon on the surface of the third film by adopting a chemical vapor deposition method to form a fourth film, and further forming the substrate infrared anti-reflection protective film.
Wherein, the ion source assisted evaporation deposition film forming step comprises: evaporating the germanium film material by using an electron gun, and depositing to form a first film, wherein the extraction voltage of an electron beam is 5-10kV, the evaporation beam current is 200-350mA, and the evaporation rate is 0.1-0.2 nm/s;
wherein, the ion-assisted evaporation deposition film-forming step comprises: evaporating zinc sulfide film material by using an electron gun, depositing to form a second film, wherein the electron beam extraction voltage is 5-10kV, the evaporation beam current is 15-25mA, and the evaporation rate is 0.3-0.5 nm/s.
Wherein, the ion source assisted evaporation deposition film forming step comprises: and evaporating the germanium film material by using an electron gun, depositing to form a third film, leading out the high voltage of 5-10kV by using an electron beam, leading the evaporation beam current to be 100-300mA, and leading the evaporation rate to be 0.1-0.2 nm/s.
Wherein, the step of forming the film by chemical vapor deposition comprises the following steps: and introducing argon gas of 20-25sccm and n-butane of 10-18sccm into the chemical vapor deposition equipment, and depositing for 20-25 min.
Wherein the step of turning on the ion assist environment comprises: and introducing argon gas with the flow of 30-40sccm into the ion source environment, starting the ion source, and adjusting the beam current of the ion source to be 45-55 mA.
Wherein, an interval of 3-5 minutes is arranged between the step of opening the ion auxiliary environment and the step of ion auxiliary evaporation deposition film formation, and an interval of 3-5 minutes is arranged between the step of ion auxiliary evaporation deposition film formation and the step of closing the ion auxiliary environment; the environmental temperature in the ion-assisted evaporation coating step is 140-150 ℃.
In the invention, considering the requirement of the zinc sulfide substrate on the mechanical damage resistance, the outermost layer is a diamond-like (D L C) film, because the D L C film has poor bonding strength on the zinc sulfide substrate and high bonding strength with the germanium film, the germanium film is selected between the D L C film and the zinc sulfide substrate, and the four film layers and the sequence and thickness of the four film layers are arranged, so that the infrared anti-reflection protective film of the substrate achieves the ideal transmittance and mechanical damage resistance.
The invention has the following beneficial effects:
1. the average transmittance of the multispectral ZnS substrate in the wave band ranges of 7-12 mu m and 8-10 mu m can respectively reach 85.4% and 90.4%, and the problem that the film firmness, the transmittance and the higher mechanical damage resistance cannot be considered at the same time is solved.
2. The preparation method of the multispectral ZnS substrate has the advantages of simple process, no pollution and low cost.
Drawings
Various other advantages and benefits will become apparent to those of ordinary skill in the art upon reading the following detailed description of the preferred embodiments. The drawings are only for purposes of illustrating the preferred embodiments and are not to be construed as limiting the invention. Also, like reference numerals are used to refer to like parts throughout the drawings. In the drawings:
FIG. 1 shows a schematic view of a base infrared antireflective protective film according to an embodiment of the invention;
FIG. 2 shows a graph of transmittance analysis of a substrate infrared antireflective coating according to an embodiment of the invention.
Detailed Description
Exemplary embodiments of the present disclosure will be described in more detail below with reference to the accompanying drawings. While exemplary embodiments of the present disclosure are shown in the drawings, it should be understood that the present disclosure may be embodied in various forms and should not be limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the disclosure to those skilled in the art.
As shown in fig. 1, the multispectral ZnS substrate infrared anti-reflection film is plated on the surface of the multispectral ZnS optical component, and the anti-reflection protective film has a structure of a first film 110, a second film 120, a third film 130 and a fourth film 140, wherein the first film 110 is plated on the surface of the multispectral ZnS substrate 100de, the first film 110 is a Ge film, the second film 120 is a ZnS film, the third film 130 is a Ge film, and the fourth film 140 is a D L C film.
As the scheme of the multispectral ZnS substrate infrared anti-reflection protective film, the thickness of the first layer 110 is 200-220nm, the thickness of the second layer 120 is 480-500nm, the thickness of the third layer 130 is 280-300nm, and the thickness of the fourth layer 140 is 1200-1300 nm.
Meanwhile, the invention also discloses a preparation method of the ZnS substrate infrared anti-reflection protective film, which comprises the following steps:
1) depositing a first layer of film on the multispectral ZnS substrate at the speed of 0.1-0.2nm/s by adopting an ion beam assisted evaporation method, 2) depositing a second layer of film on the first layer of film at the speed of 0.3-0.5nm/s by adopting the ion beam assisted evaporation method, 3) depositing a third layer of film on the second layer of film at the speed of 0.1-0.2nm/s by adopting the ion beam assisted evaporation method, 4) depositing a D L C film on the third layer of film by adopting a CVD method, wherein the deposition time is 20-25 min.
Specifically, when the first layer of film is prepared in the step 1), an electron gun or a tungsten boat is adopted to heat the evaporation film material Ge, the evaporation beam current is 200-220 mA, and the first layer of film is deposited on the multispectral ZnS substrate at the speed of 0.1-0.2nm/s, wherein the thickness of the first layer of film is 200-220 nm.
In the step 2), the second film is prepared by heating the evaporation film material ZnS by an electron gun or a molybdenum boat, wherein the evaporation beam current is 15-25mA, and the second film is deposited on the first film at the speed of 0.3-0.5nm/s, and the thickness is 480-500 nm.
The preparation of the third layer of film in the step 3) is specifically that an electron gun or a tungsten boat is adopted to heat the evaporation film material Ge, the evaporation beam current is 100-300mA, and the third layer of film is deposited on the second layer of film at the speed of 0.1-0.2nm/s, wherein the thickness is 280-300 nm.
Specifically, when the fourth layer film is prepared in the step 4), a CVD method is adopted, firstly, a cleaning mode is started, the gas flow is 30-45sccm of argon, and the time is 5 min. Then, a fourth layer of film is deposited on the third layer of film, the thickness is 1200-1300nm, the gas flow is 20-25sccm of argon, 10-18sccm of n-butane, and the film plating time is 20-25 min. Since the cleaning process in this step will remove part of the Ge film, the corresponding thickness should be compensated for on the basis of the theoretical value when the Ge film is deposited in step 3).
And coating a protective paint on the polished ZnS substrate, washing the protective paint before coating, soaking the ZnS substrate in analytical grade alcohol for 2 hours, taking out the ZnS substrate, and finally scrubbing the ZnS substrate clean by using a mixture of alcohol and ether.
The technical solution of the present invention will be explained in further detail by the form of specific embodiments.
Example 1 preparation method of ZnS substrate infrared antireflection protective film X1
The preparation method comprises the following steps:
s1, polishing the multispectral ZnS part, which comprises 1, polishing a multispectral ZnS flat sheet with a phi 26 × 3 surface smoothness of II grade, wherein delta N is 0.3, 2, coating a ZnS substrate with a protective paint after polishing, washing the protective paint before coating, soaking the ZnS substrate in analytically pure alcohol for 2h, taking out the ZnS substrate, and finally, cleaning the ZnS substrate with a mixture of alcohol and ether.
And S2, placing the substrate. The specific operation is as follows: circulating water, an air compressor and a main power supply are started; opening a diffusion pump for preheating, and opening an air valve to inflate the vacuum chamber; opening a vacuum chamber door, cleaning the vacuum chamber, and mainly cleaning the ion source and the electron gun; adding a film material, and replacing the crystal oscillation piece; loading the multispectral ZnS flat sheet into a fixture, and then loading the multispectral ZnS flat sheet onto a planetary disc of a film coating machine; and checking whether each part is normal or not, and checking whether the work roll and the baffle are flexible or not.
S3, vacuumizing, wherein the vacuum degree reaches 8 × 10-2Turning on a Roots pump when Pa, closing a low valve, opening a pre-valve, finally opening a high valve and pumping high vacuum when reaching 3 Pa; the vacuum degree reaches 10-2After the Pa magnitude, the furnace is started to work and is turned on and baked, and the set temperature is 140 ℃.
S4, opening and separatingAssisted by a sub-source, and particularly operated by reaching a vacuum degree of 4 × 10-3After Pa, regulating the power-on voltage to 50V to prepare for starting an ion source; opening an argon bottle pressure reducing valve, introducing argon, and setting the flow rate to be 30 sccm; and opening an ion source switch, and adjusting the ion source beam current to 45 mA.
And S5, performing ion-assisted electron evaporation coating. The specific operation is as follows: after the ion source is started for 3 minutes, evaporating a Ge film material by using an electron gun under the auxiliary condition of the ion source, evaporating and leading out high voltage of 8kV by using an electron beam, depositing a first film on the multispectral ZnS substrate at the speed of 0.1nm/s by using an evaporation beam current of 350mA, wherein the thickness of the first film is 200 nm; then, under the auxiliary condition of an ion source, evaporating ZnS film material by using an electron gun, carrying out high voltage of 5kV and an evaporation beam current of 25mA, and depositing a second film with the thickness of 500nm on the first film at the speed of 0.5 nm/s; then, under the auxiliary condition of an ion source, an electron gun is used for evaporating the Ge film material, the high voltage is 10kV, the evaporating beam current is 350mA, and a third film is deposited on the second film at the speed of 0.2nm/s, wherein the thickness of the third film is 500 nm.
And S6, closing the ion source 3 minutes after the third layer film is coated.
And S7, standing and annealing. And standing the multispectral ZnS substrate plated with the three transition layer films for 24h, and annealing.
And S8, chemical vapor deposition coating. Specifically, the cleaning mode is first started to clean the surface of the transition layer film. The cleaning gas is argon, the gas flow is 30sccm, and the cleaning time is 5 min. The deposition of a fourth layer of film was then started on top of the third layer of film to a thickness of 1300 nm. In the deposition process, the gas flow is 25sccm of argon, 10sccm of n-butane and the deposition time is 25 min. And after the film coating is finished, forming a ZnS substrate infrared anti-reflection protective film A.
The performance of the prepared multispectral ZnS substrate infrared anti-reflection protective film A is tested, and the test result is as follows.
1. Infrared transmittance: fig. 2 is an actually measured spectrum curve of the multispectral ZnS substrate infrared antireflection protective film a, as shown in fig. 2, the average transmittances of the multispectral ZnS substrate infrared antireflection protective film a in the wavelength ranges of 7-12 μm and 8-10 μm are 85.4% and 90.4%, respectively.
2. The severe environment resistance performance: the multispectral ZnS substrate infrared anti-reflection protective film A is tested as follows, and the test result shows that the film has no obvious phenomena of cracking, demoulding and the like, and the optical performance of the film is kept unchanged.
① high and low temperature tests, at-50 deg.C and 100 deg.C for 4 hr respectively, wherein the humidity at 100 deg.C is 95%, and the test lasts for 5 times.
② soaking in pure water for 30 days.
③ soaking in saline for 10 days.
④ tape test, using 3M tape, was adhered to the surface of the film and then pulled off with force.
Example 2 preparation method of ZnS substrate infrared antireflection protective film X2
The preparation method comprises the following steps:
s1, polishing the multispectral ZnS part, which comprises 1, polishing a multispectral ZnS flat sheet with a phi 26 × 3 surface smoothness of II grade, wherein delta N is 0.3, 2, coating a ZnS substrate with a protective paint after polishing, washing the protective paint before coating, soaking the ZnS substrate in analytically pure alcohol for 2h, taking out the ZnS substrate, and finally, cleaning the ZnS substrate with a mixture of alcohol and ether.
And S2, placing the substrate. The specific operation is as follows: circulating water, an air compressor and a main power supply are started; opening a diffusion pump for preheating, and opening an air valve to inflate the vacuum chamber; opening a vacuum chamber door, cleaning the vacuum chamber, and mainly cleaning the ion source and the electron gun; adding a film material, and replacing the crystal oscillation piece; loading the multispectral ZnS flat sheet into a fixture, and then loading the multispectral ZnS flat sheet onto a planetary disc of a film coating machine; and checking whether each part is normal or not, and checking whether the work roll and the baffle are flexible or not.
S3, vacuumizing, wherein the vacuum degree reaches 8 × 10-2Turning on a Rotz pump when PB reaches 3PB, closing a low valve, opening a pre-valve, finally opening a high valve, and pumping high vacuum; the vacuum degree reaches 10-2After PB level, start working and bake, and set the temperature at 150 ℃.
S4, turning on the ion source assist, the operation is that the vacuum degree reaches 4 × 10-3After PB, the power-on voltage is adjusted to 50V to prepare for openingA sub-source; opening an argon bottle pressure reducing valve, introducing argon, and setting the flow rate to be 40 sccm; and opening an ion source switch, and adjusting the ion source beam current to 55 mA.
And S5, performing ion-assisted electron evaporation coating. The specific operation is as follows: after the ion source is started for 5 minutes, evaporating a Ge film material by using an electron gun under the auxiliary condition of the ion source, evaporating and leading out high voltage of 10kV by using an electron beam, depositing a first film on the multispectral ZnS substrate at the speed of 0.2nm/s by using an evaporation beam current of 200mA, wherein the thickness of the first film is 220 nm; then, under the auxiliary condition of an ion source, evaporating ZnS film material by using an electron gun, carrying out high voltage of 5kV and an evaporation beam current of 15mA, and depositing a second film with the thickness of 480nm on the first film at the speed of 0.3 nm/s; then, under the auxiliary condition of an ion source, an electron gun is used for evaporating the Ge film material, the high voltage is 5kV, the evaporation beam current is 200mA, and a third film is deposited on the second film at the speed of 0.1nm/s, wherein the thickness of the third film is 480 nm.
And S6, closing the ion source 5 minutes after the third layer film is coated.
And S7, standing and annealing. And standing the multispectral ZnS substrate plated with the three transition layer films for 48h, and annealing.
And S8, chemical vapor deposition coating. Specifically, the cleaning mode is first started to clean the surface of the transition layer film. The cleaning gas is argon, the gas flow is 45sccm, and the cleaning time is 5 min. Then, the deposition of a fourth film was started on the third film to a thickness of 1200 nm. During the deposition process, the gas flow rate is 20sccm of argon, 18sccm of n-butane and the deposition time is 20 min. And after the film coating is finished, forming a ZnS substrate infrared anti-reflection protective film B.
And (3) carrying out performance test on the prepared multispectral ZnS substrate infrared anti-reflection protective film B, wherein the test result is as follows.
1. The average transmittance of the multispectral ZnS substrate infrared anti-reflection protective film B in the wave band ranges of 7-12 μm and 8-10 μm is 85.4% and 90.4% respectively.
2. The severe environment resistance performance: the multispectral ZnS substrate infrared anti-reflection protective film B is tested as follows, and the test result shows that the film has no obvious phenomena of cracking, demoulding and the like, and the optical performance of the film is kept unchanged.
① high and low temperature tests, at-50 deg.C and 100 deg.C for 4 hr respectively, wherein the humidity at 100 deg.C is 95%, and the test lasts for 5 times.
② soaking in pure water for 30 days.
③ soaking in saline for 10 days.
④ tape test, using 3M tape, was adhered to the surface of the film and then pulled off with force.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.
Claims (10)
1. The infrared anti-reflection protective film for the substrate is characterized by comprising the substrate (100) and a first layer of film (110), a second layer of film (120), a third layer of film (130) and a fourth layer of film (140) which are arranged layer by layer from the surface of the substrate (100), wherein the first layer of film (110) and the third layer of film (130) are both germanium films, the second layer of film (120) is a zinc sulfide film, and the fourth layer of film (140) is a diamond-like film.
2. The substrate infrared antireflective protective film of claim 1,
the first layer (110) has a thickness of 200-.
3. The substrate infrared antireflective protective film of claim 1,
the substrate (100) is a multi-spectral zinc sulfide substrate.
4. A method of making a protective infrared antireflective film according to any one of claims 1 to 3, comprising the steps of:
putting the substrate into a closed film-making environment;
vacuumizing the film preparation environment;
starting an ion source in a vacuum film-making environment;
in an ion-assisted vacuum film-making environment, depositing a germanium raw material, a zinc sulfide raw material and a germanium raw material on the surface of a substrate in sequence by adopting an evaporation method, and forming a first film, a second film and a third film in sequence;
turning off the ion source;
and in the vacuum film-making environment without ion assistance, depositing carbon on the surface of the third film by adopting a chemical vapor deposition method to form a fourth film, and further forming the substrate infrared anti-reflection protective film.
5. The method of claim 4, wherein the ion source assisted vapor deposition film forming step comprises:
and evaporating the germanium film material by using an electron gun, and depositing to form a first film, wherein the extraction voltage of an electron beam is 5-10kV, the evaporation beam current is 200-350mA, and the evaporation rate is 0.1-0.2 nm/s.
6. The method of claim 4, wherein the ion assisted vapor deposition film forming step comprises:
evaporating zinc sulfide film material by using an electron gun, depositing to form a second film, wherein the electron beam extraction voltage is 5-10kV, the evaporation beam current is 15-25mA, and the evaporation rate is 0.3-0.5 nm/s.
7. The method of claim 4, wherein the ion source assisted vapor deposition film forming step comprises:
and evaporating the germanium film material by using an electron gun, depositing to form a third film, leading out the high voltage of 5-10kV by using an electron beam, leading the evaporation beam current to be 100-300mA, and leading the evaporation rate to be 0.1-0.2 nm/s.
8. The production method according to claim 4, wherein the step of chemical vapor deposition film formation comprises:
and introducing argon gas of 20-25sccm and n-butane of 10-18sccm into the chemical vapor deposition equipment, and depositing for 20-25 min.
9. The method of claim 4, wherein the step of turning on the ion source comprises:
and introducing argon gas with the flow of 30-40sccm into the ion source environment, starting the ion source, and adjusting the beam current of the ion source to be 45-55 mA.
10. The method according to claim 4,
an interval of 3-5 minutes is arranged between the step of opening the ion auxiliary environment and the step of ion auxiliary evaporation deposition film formation, and an interval of 3-5 minutes is arranged between the step of ion auxiliary evaporation deposition film formation and the step of closing the ion auxiliary environment; the environmental temperature in the ion-assisted evaporation coating step is 140-150 ℃.
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