CN112251137B - Crystal coating film element, preparation method thereof and crystal film system - Google Patents
Crystal coating film element, preparation method thereof and crystal film system Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
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- Surface Treatment Of Optical Elements (AREA)
Abstract
The application relates to the field of laser materials, in particular to a crystal coating film element, a preparation method thereof and a crystal film system. The crystal coating element includes: crystal baseA bottom; a matching film covered on the crystal substrate, wherein the matching film is made of polymethyl siloxane and SiO2A mixture of (a); and the anti-reflection film is covered on the matching film, and the material of the anti-reflection film comprises SiO2(ii) a Polymethylsiloxane and SiO2After mixing, curing to form a matching film, wherein the polymethylsiloxane is attached to the surface of the crystal during film formation, and the organic chain-like flexible structure of the polymethylsiloxane is beneficial to inhibiting the film cracking effect caused by the thermal expansion of the crystal; SiO 22The introduction of the particles can improve the mechanical property and the thermal stability of the matching film; the thermal expansion coefficient of the obtained matching film is between that of the crystal substrate and the antireflection film, so that the matching film with better physical and chemical properties is formed, and the problem that the antireflection film is easy to crack is solved.
Description
Technical Field
The application relates to the field of laser materials, in particular to a crystal coating film element, a preparation method thereof and a crystal film system.
Background
The high-power solid laser is an experimental means necessary for laser fusion, high-energy density physics and advanced basic science research. The research of laser-driven Inertial Confinement Fusion (ICF) has become a major advanced scientific and technological field, and is a main technical approach for researching the ICF and high energy density physics (HEDS) in laboratories without alternatives, and is one of the main technical approaches for human beings to create sustainable energy in the future. Laser fusion requires a sufficiently high energy and power to drive the laser pulse, while also requiring high beam quality.
Optical Parametric Chirped Pulse Amplification (OPCPA) technique. The OPCAP technology replaces the traditional gain medium in the laser amplifier with the nonlinear crystal, and requires the crystal to have high transmittance to the pump light, the signal light and the idler frequency light, excellent phase matching performance, high conversion efficiency, wide parametric gain bandwidth, high laser damage threshold and the like, and the development of the optical parametric amplification technology depends on and depends on the development of the nonlinear amplification crystal to a great extent.
In order to reduce the optical energy loss and parasitic feedback phenomenon caused by Fresnel reflection and improve the output efficiency of the intense laser device, antireflection films meeting different working wavelengths must be deposited on the surface of the crystal before use.
However, the film layer is easy to break under the action of the thermal stress of the substrate, and particularly for materials with large difference of thermal expansion coefficients in all directions, the change of all directions changes along with the change of the temperature of crystals, so that the film coating on the crystals is more difficult; the film layer is broken more, and the service life and the laser power resistance of the film layer are directly influenced.
Disclosure of Invention
An object of the embodiments of the present invention is to provide a crystal coating film element, a method for manufacturing the same, and a crystal film system, which are intended to solve the problem that a conventional crystal film layer is likely to crack.
The present application provides a crystal coating film element, including:
a crystal substrate;
a matching film covered on the crystal substrate, wherein the matching film is made of polymethyl siloxane and SiO2A mixture of (a); and
the anti-reflection film covers the matching film, and the material of the anti-reflection film comprises SiO2；
Wherein the weight average molecular weight of the polymethylsiloxane is 8000 of 5000-.
Polymethylsiloxane and SiO2After mixing, curing to form a matching film, wherein the polymethylsiloxane is attached to the surface of the crystal during film formation, and the organic chain-like flexible structure of the polymethylsiloxane is beneficial to inhibiting the film cracking effect caused by the thermal expansion of the crystal; SiO 22The introduction of the particles can improve the mechanical property and the thermal stability of the matching film; the thermal expansion coefficient of the obtained matching film is between that of the crystal substrate and the antireflection film, so that the matching film with better physical and chemical properties is formed, and the problem that the antireflection film is easy to crack is solved.
In some embodiments of the first aspect of the present application, the crystalline coating film element further comprises at least one buffer film located between the matching film and the antireflective film; the buffer film is made of polymethyl siloxane and SiO2A mixture of (a);
optionally, the refractive indices of the buffer film and the matching film are different;
optionally, the refractive index of each layer of the buffer film is not completely the same;
optionally, the crystal coating element comprises a plurality of antireflection films, each of which has a refractive index that is not completely the same.
In some embodiments of the first aspect of the present application, the crystalline substrate material is lithium triborate crystals, beta phase barium metaborate crystals, or potassium dihydrogen phosphate crystals.
In some embodiments of the first aspect of the present application, the matching film has a film thickness of 110-120nm, and the matching film has a refractive index of 1.35-1.44; the film thickness of the antireflection film is 130-137nm, and the refractive index of the antireflection film is 1.12-1.25;
optionally, the film thickness of the matching film is 113.2nm, and the refractive index of the matching film is 1.42; the film thickness of the antireflection film is 134.3nm, and the refractive index of the antireflection film is 1.19.
The matching film and the antireflection film with the film thickness and the refractive index can realize that the transmittance of the element coated with the LBO crystal substrate reaches 99.5 percent at 527nm and the broadband transmittance within the wave band range of (800 +/-50) nm reaches more than 99 percent.
In a second aspect, the present application provides a method for preparing a crystal coated film element, comprising:
mixing the mixture containing polymethylsiloxane and SiO2The first sol is solidified to obtain a matching film after forming a film on the surface of a crystal substrate;
then will contain SiO2The second sol is solidified to obtain the anti-reflection film after forming a film on the surface of the matching film;
wherein the weight average molecular weight of the polymethylsiloxane is 8000 of 5000-.
The preparation method can improve the problem of film cracking, and can be used for preparing crystal element films with different refractive indexes; the target refractive index of the film layer can be adjusted according to the relationship between the refractive index of the substrate and the refractive indexes of the substrate and the film layer, and crystal coating elements meeting different working wavelengths are prepared on the surfaces of different crystal substrates.
In some embodiments of the second aspect of the present application, forming the matching film further comprises, before forming the antireflective film: forming at least one layer of buffer film on the surface of the matching film;
wherein the preparation step of the buffer film comprises the following steps: mixing the mixture containing polymethylsiloxane and SiO2Curing the third sol to obtain the buffer film;
optionally, the polymethylsiloxane and the SiO in the first sol and the third sol2The proportions of (A) and (B) are different;
optionally, the polymethylsiloxane and the SiO in a third sol used for preparing each layer of the buffer film2Are different.
In some embodiments of the second aspect of the present application, the matching film has a film thickness of 110-120nm, and the matching film has a refractive index of 1.35-1.44; the film thickness of the antireflection film is 130-137nm, and the refractive index of the antireflection film is 1.12-1.25;
optionally, the film thickness of the matching film is 113.2nm, and the refractive index of the matching film is 1.42; the film thickness of the antireflection film is 134.3nm, and the refractive index of the antireflection film is 1.19.
In some embodiments of the second aspect of the present application, the first sol is SiO2The particle size of the (B) is 55-78 nm, and the viscosity is 1.82-1.98 cp;
optionally, SiO in the second sol2The particle size of the (B) is 55-70 nm, and the viscosity is 1.64-1.69 cp;
optionally, the polymethylsiloxane and SiO in the first sol2The mass ratio of (1) to (0.1-2).
In some embodiments of the second aspect of the present application, the polymethylsiloxane is prepared by:
heating the mixture of methyltriethoxysilane, anhydrous ethanol and water to 75-85 deg.C, adding 45-50 wt% ethanol water solution when the liquid begins to boil, mixing, refluxing for 15-25 hr, and removing ethanol.
A third aspect of the present application provides a crystal film system including:
the matching film is made of polymethyl siloxane and SiO2A mixture of (a); and
the anti-reflection film covers the surface of the matching film, and the material of the anti-reflection film comprises SiO2；
Wherein the weight average molecular weight of the polymethylsiloxane is 8000 of 5000-;
optionally, the crystal film system further includes a buffer film, the buffer film is located between the anti-reflection film and the matching film, and the buffer film is made of polymethylsiloxane and SiO2A mixture of (a).
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are required to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present application and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained from the drawings without inventive effort.
FIG. 1 shows a graph of the results of a polymethylsiloxane gel permeation chromatography test;
FIG. 2 shows a nuclear magnetic spectrum of polymethylsiloxane;
FIG. 3 is a view showing the appearance of an LBO crystal coated member provided in example 1;
FIG. 4 shows AFM photographs of the matching films, respectively;
FIG. 5 shows an AFM photograph of an antireflective film;
FIG. 6 shows an LBO crystal coating element measured overall transmittance curve versus a design curve;
fig. 7 shows an appearance of the LBO crystal coated member of comparative example 1.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions of the embodiments of the present application will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
In the OPCPA system, a commonly used nonlinear crystal is LBO (LiB)3O5Lithium triborate), BBO (. beta. -BaB)2O4Beta phase barium metaborate), KDP (KH)2PO4Potassium dihydrogen phosphate), wherein the laser damage threshold of the LBO crystal is the highest among the commonly used inorganic nonlinear optical crystals (see table 1); meanwhile, the LBO crystal has wide light-transmitting wave band, is slightly deliquescent, has good physical and chemical properties, good optical uniformity, moderate nonlinear optical coefficient, small discrete angle and wide acceptance angle, and is widely applied to a strong laser device to realize the nonlinear optical frequency conversion function.
TABLE 1 comparison of Damage thresholds for several commonly used nonlinear crystals
In order to reduce the optical energy loss and parasitic feedback phenomenon caused by Fresnel reflection and improve the output efficiency of the intense laser device, antireflection films meeting different working wavelengths must be deposited on the surface of the crystal before use.
Crystalline coatings are more difficult to apply than coatings on conventional substrates (e.g., quartz, BK7), primarily because the thermal stress generated by the coating is very likely to crack the coating, which directly affects the life of the film and the resistance to laser damage.
In particular, with LBO crystals, the difference in thermal expansion coefficient (α) is large due to the characteristics of the LBO crystals themselves, such as anisotropy, especiallyx＝10.8×10-5/K,αy＝8.8×10-5/K,αz＝3.4×10-5and/K), and the change in anisotropy changes with the change in crystal temperature, the coating film is more difficult and cracks are likely to occur.
In order to improve the above problems, the present application provides a crystal coating film element and a corresponding manufacturing method, and the following describes the crystal coating film element, the manufacturing method thereof, and the crystal film system in the embodiments of the present application.
A crystal coated membrane element, comprising:
a crystal substrate;
a matching film covered on the crystal substrate, wherein the matching film is made of polymethyl siloxane and SiO2A mixture of (a); and
the anti-reflection film is covered on the matching film and made of SiO2。
Wherein the weight average molecular weight of the polymethylsiloxane is 8000 of 5000-.
The crystal coating film element comprises a crystal substrate, a matching film and an anti-reflection film, wherein the matching film is positioned between the crystal substrate and the anti-reflection film, and the matching film is made of polymethyl siloxane and SiO2A mixture of (a).
Polymethylsiloxane and SiO2After mixing, curing to form a matching film, wherein the polymethylsiloxane is attached to the surface of the crystal during film formation, and the organic chain-like flexible structure of the polymethylsiloxane is beneficial to inhibiting the film cracking effect caused by the thermal expansion of the crystal; SiO 22The introduction of the particles can improve the mechanical property and the thermal stability of the matching film; the thermal expansion coefficient of the obtained matching film is between the crystalA matching film with better physical and chemical properties is formed between the body substrate and the anti-reflection film, so that the problem that the anti-reflection film is easy to crack is solved.
Illustratively, the material of the crystal substrate may be LBO, BBO, or KDP.
Illustratively, when the material of the crystal substrate can be LBO (lithium triborate crystal), the film thickness of the matching film is 110-120nm, and the refractive index of the matching film is 1.35-1.44; the film thickness of the antireflection film is 130-137nm, and the refractive index of the antireflection film is 1.12-1.25.
In an OPCPA system for amplifying 800nm signal light by 527nm pump light parameters, the maximum parameter bandwidth of about 100nm is required to be obtained, namely, the spectrum of the coated crystal element can meet the requirement of simultaneous anti-reflection of 527nm single wavelength pump light and 800 +/-50 nm wide wavelength band signal light, and the preparation requirement of a broadband antireflection film is provided for a strong laser LBO crystal coating element. The quality of the optical film coated on the surface of the intense laser crystal element determines the load intensity, reliability and beam quality of the laser system operation to a great extent.
Illustratively, when the material of the crystal substrate is LBO (lithium triborate crystal), the film thickness of the matching film is 110-120nm, and the refractive index of the matching film is 1.35-1.44; the film thickness of the antireflection film is 130-137nm, and the refractive index of the antireflection film is 1.12-1.25.
For example, the film thickness of the matching film may be 110nm, 112nm, 113nm, 113.2nm, 114nm, 116nm, 118nm, or 120nm, the refractive index of the matching film may be 1.36, 1.38, 1.40, 1.41, 1.42, or 1.44, and so forth. The film thickness of the antireflection film may be 130nm, 131nm, 133nm, 134.3nm, 135nm, 137nm, or the like, and the refractive index of the antireflection film may be 1.12, 1.19, 1.20, 1.21, 1.23, 1.25, or the like.
The matching film and the antireflection film with the film thickness and the refractive index can realize that the transmittance of the element coated with the LBO crystal substrate reaches 99.5 percent at 527nm and the broadband transmittance within the wave band range of (800 +/-50) nm reaches more than 99 percent.
The refractive index of the matching film can be adjusted by adjusting the composition of the material, for example, adjusting the thickness of the polymethyl siliconSiloxane and SiO2The ratio of (a) to (b). The refractive index of the antireflection film can be improved by preparing SiO with different porosities2And adjusting the hollow ball.
In other words, two films, one matching film and one antireflection film are prepared on the crystal substrate, the film thickness of the matching film is 110-120nm, and the refractive index of the matching film is 1.35-1.44; the film thickness of the antireflection film is 130-137nm, and the refractive index of the antireflection film is 1.12-1.25. The crystal coating element has better crack resistance, and the transmittance at 527nm reaches 99.5 percent, and the broadband transmittance within the wave band range of (800 +/-50) nm reaches more than 99 percent. The problem of film cracking caused by the anisotropy of the LBO crystal after film forming is effectively solved, the service life of the film is prolonged, and the guarantee is provided for the continuous output of high-power energy of a strong laser device.
In other embodiments of the present application, in which the crystal substrate is BBO or KDP, the element can be anti-reflective over a single wavelength and a broad wavelength range, with superior broadband transmission.
In addition, the crystal coating element can realize the functions only through one matching film and one antireflection film, can improve the element coating efficiency, and can reduce chemical pollution caused by mutual permeation among chemical films.
Further, in some embodiments of the present application, the refractive index of the matching film and the refractive index and the thickness of the antireflection film in the crystal coating element may also be other values, for example, designed according to different usage approaches and different usage scenarios of the crystal coating element.
Further, in some embodiments of the present application, the crystal coating element may further include at least one buffer film; the at least one layer of buffer film is positioned between the matching film and the antireflection film, and the buffer film is made of polymethyl siloxane and SiO2A mixture of (a).
When the crystal coated film element is used in the course of some other scenes, at least one buffer film may be formed between the matching film and the antireflection film according to the design requirements for the films in the crystal coated film element.
The buffer film is made of polymethyl siloxane and SiO2Of (a) and, correspondingly, polymethylsiloxane and SiO2The cracking of the anti-reflection film can be avoided under the interaction.
The buffer film may also be used to adjust the overall refractive index of the film layer, and thus the refractive indices of the buffer film and the matching film may not be the same, and the refractive indices of each of the buffer films may not be exactly the same.
Accordingly, in some embodiments of the present application, a crystal coated film element includes a plurality of the antireflective films, each of which has a refractive index that is not exactly the same.
The crystal coating element provided by the embodiment of the application has at least the following advantages:
the material is polymethyl siloxane and SiO2A matching film of the mixture of (1), polymethylsiloxane-modified SiO2So that the matching membrane has good physicochemical properties. The polymethyl siloxane is attached to the surface of the crystal, the unique molecular structure of the polymethyl siloxane can avoid the problem of film cracking caused by larger difference of thermal expansion coefficients of the crystal and the antireflection film, and SiO2The mechanical property and the thermal stability of the matching film are improved. Even if the crystal material is anisotropic lithium triborate crystal, the crystal coating element provided by the embodiment of the application can effectively inhibit the film cracking phenomenon caused by the difference of the anisotropic thermal expansion coefficients.
Furthermore, through the design of the thickness and the refractive index of the antireflection film and the matching film, the transmittance of the crystal element at 527nm reaches 99.5 percent, and the broadband transmittance within the wavelength range of (800 +/-50) nm reaches more than 99 percent, so that the laser damage threshold of the crystal element is improved.
The present application also provides a crystal film system, which includes:
the matching film is made of polymethyl siloxane and SiO2A mixture of (a); and
at least one anti-reflection film layer covering the surface of the matching film, wherein the anti-reflection film layer is made of SiO2. Wherein the weight average molecular weight of the polymethylsiloxane is 8000 of 5000-.
In some embodiments, the crystal film system further comprises a buffer film located at the antireflection layerBetween the film and the matching film, the buffer film is made of polymethyl siloxane and SiO2A mixture of (a).
Please refer to the above description of the crystal coating device, the crystal film in the present application is a portion of the crystal coating device not including the crystal substrate, and is not described herein again.
The application also provides a preparation method of the crystal coated film element, which comprises the following steps:
mixing the mixture containing polymethylsiloxane and SiO2The first sol is solidified to obtain a matching film after forming a film on the surface of a crystal substrate;
then will contain SiO2The second sol is solidified to obtain the anti-reflection film after forming the film on the surface of the matching film. Wherein the weight average molecular weight of the polymethylsiloxane is 8000 of 5000-.
Forming a matching film on the surface of a crystal substrate; mainly comprises the following components of polymethylsiloxane and SiO2And mixing the sol with a solvent to prepare a first sol, and solidifying the first sol after forming a film on the surface of the crystal substrate.
In an embodiment of the present application, the solvent may include at least one of ethanol, methanol, butanol, and heptane. And the solvent is volatilized in the curing process, and the finally obtained matching film does not contain the solvent.
In the examples of the present application, polymethylsiloxane, SiO2The sol can be obtained in a commercially available mode, or the first sol is directly commercially available; molecular weight of polymethylsiloxane, refractive index after film formation thereof, and SiO2The particle size and refractive index of (b) can be selected according to the requirements of the crystal coated device.
For example, for the embodiment in which the substrate of the crystal coating element is lithium triborate crystal, the film thickness of the matching film is 110-120nm, and the refractive index of the matching film is 1.35-1.44; the film thickness of the antireflection film is 130-137nm, and the refractive index of the antireflection film is 1.12-1.25.
Under the range, the crystal coating element obtained by the preparation method has better crack resistance, and meanwhile, the transmittance at 527nm reaches 99.5 percent, and the broadband transmittance within the wave band range of (800 +/-50) nm reaches more than 99 percent.
Optionally, the film thickness of the matching film is 113.2nm, and the refractive index of the matching film is 1.42; the film thickness of the antireflection film is 134.3nm, and the refractive index of the antireflection film is 1.19.
As an example, in order to obtain the above matching film, materials satisfying the following conditions may be selected: the weight average molecular weight of the polymethylsiloxane is about 5500-6500; SiO in the first sol2The particle size of (B) is 55-78 nm, and the viscosity is 1.82-1.98 cp.
SiO in the second sol2The particle size of the (B) is 55-70 nm, and the viscosity is 1.64-1.69 cp;
optionally, the polymethylsiloxane and SiO in the first sol2The mass ratio of (1) to (0.1-2). For example, the polymethylsiloxane and SiO in the first sol2The mass ratio of (b) may be 1:0.1, 1: 0.5, 1:0.9, 1:1.2, 1:1.4, or 1:2, and so forth.
The anti-reflection film and the matching film prepared from the raw materials have better toughness.
Illustratively, the present embodiment provides a lower index of refraction SiO2The sol preparation method of (1).
The method comprises the following steps: tetraethyl orthosilicate, ethanol and 28-35% ammonia water are selected, stirred and aged for 18-20 days, and the ammonia is removed to obtain SiO2And (3) sol. It is understood that the ethanol may be replaced by other low boiling point solvents such as methanol.
For example, 208g of purified tetraethyl orthosilicate, 1084g of absolute ethanol, and 37.4g of 35% aqueous ammonia were added to a reaction flask, and stirred for 6 hours. Sealing and aging for 18-20 days, and performing decompression reflux for more than 10 hours after aging to remove ammonia to obtain SiO2And (3) sol.
In this example, the polymethylsiloxane was prepared by the following method:
heating mixture of methyltriethoxysilane, anhydrous ethanol and water to 75-85 deg.C (such as 75 deg.C, 78 deg.C, 80 deg.C, 82 deg.C, 85 deg.C, etc.), adding 45-50 wt% ethanol water solution when liquid begins to boil, mixing, refluxing for 15-25 hr, and removing ethanol.
Further, in the mixture of methyltriethoxysilane, anhydrous ethanol and water, the ratio of methyltriethoxysilane, anhydrous ethanol and water may be, for example: 17, (2-3) and (5-6); the mass ratio of the ethanol aqueous solution to the methyltriethoxysilane can be 17 (3.5-4.5).
For example, 1783g of Methyltriethoxysilane (MTES), 266.8g of absolute ethanol and 586.8g of deionized water were added to the reactor, respectively, heated to 80 ℃ and a mixture of 198g of deionized water and 184g of ethanol was added when the liquid in the reactor began to boil. Refluxing for about 20h, and beginning to distill ethanol in the reactor to ensure that the final mass fraction of the polymethylsiloxane is about 33 percent to obtain the polymethylsiloxane. The weight average molecular weight Mw thereof is 6130.
In the present example, the above-mentioned polymethylsiloxane and SiO are used2The method for preparing the first sol is as follows:
mixing 1000mL of the polymethylsiloxane, 1000mL of n-butanol and 5000mL of absolute ethanol, and stirring for more than 8 hours; by controlled addition of SiO2The addition amount of the sol adjusts the refractive index of the final matching film. When the addition amount is 3000mL, the refractive index of the matching film reaches 1.4188. The finished sol was compounded and filtered through a 0.2 μm pore size filter to give a first sol.
It should be noted that, in other embodiments of the present application, SiO is used2Polymethylsiloxanes are commercially available. The SiO is then adjusted according to the refractive index of the final matching film2The ratio of polymethylsiloxane.
In this embodiment, the preparation method of the second sol includes:
tetraethyl orthosilicate, ethanol and 28-35% ammonia water are selected and stirred for 3-4h, and aged for 3-5 days to remove ammonia.
For example, 208g of purified tetraethyl orthosilicate, 1610g of absolute ethanol, and 51.4g of 30% aqueous ammonia were added to a reaction flask, and the mixture was stirred for 3 hours. Sealing and aging for 3-5 days, decompressing and refluxing for more than 10 hours after aging is finished, removing ammonia, and obtaining SiO with solid content of about 3.3 percent2The anti-reflection coating sol has an anti-reflection coating refractive index of about 1.1854Before use, filtration was carried out using a filter element with a pore size of 0.2 μm.
It should be noted that, in other embodiments of the present application, the second sol may also be directly SiO with a predetermined refractive index2And (5) carrying out configuration.
The film formation process is as follows:
and manually cleaning the crystal by respectively using n-butanol and toluene, and airing in a drying cabinet for more than 8 hours after cleaning.
Forming a matching film with a preset thickness (for example 113.2nm) on the surface of the crystal by adopting the first sol by changing the pulling speed of the matching film; keeping the temperature at 140 ℃ for 24 h; the pulling rate is adjusted to form a predetermined thickness (e.g., 134.3nm) on the surface of the matching film using the first sol.
In order to improve the bonding force between the film layers and improve the damage threshold of the element, the element prepared by the antireflection film is subjected to heat treatment at 160 ℃ for 24 hours.
In some other embodiments of the present application, other techniques may be used to produce antireflective films, matching films of other refractive indices and other film thicknesses.
Further, in some other embodiments of the present application, at least one buffer film may be formed between the matching film and the antireflection film according to design requirements; in detail, before forming the antireflection film after the matching film, the method further includes: forming at least one layer of buffer film on the surface of the matching film;
wherein the preparation step of the buffer film comprises the following steps: mixing the mixture containing polymethylsiloxane and SiO2And curing the third sol to obtain the buffer film.
In other words, the buffer film is positioned between the matching film and the antireflection film, the buffer film is prepared before the antireflection film is prepared, and the overall refractive index of the film layer can be adjusted to be well matched with the refractive index of the crystal through the mutual matching of the buffer film, the antireflection film and the matching film, so that the high transmission of the crystal element is realized.
Adjusting the polymethylsiloxane and SiO in the third sol according to the requirement2The ratio of (a); in some embodiments, the first sol and the third sol may not have the same content of the polymethylsiloxane.
In some embodiments, the amount of the polymethylsiloxane in the third sol used to prepare each buffer film is not exactly the same.
The preparation method of the crystal coating element provided by the embodiment of the application has at least the following advantages:
the preparation method can improve the problem of film cracking, and can be used for preparing crystal element films with different refractive indexes; the target refractive index of the film layer can be adjusted according to the relationship between the refractive index of the substrate and the refractive indexes of the substrate and the film layer, and crystal coating elements meeting different working wavelengths are prepared on the surfaces of different crystal substrates.
In addition, the method provided by the application adopts a sol-gel curing film-forming method, and the obtained film layer is loose and porous, has low density and low thermal conductivity; when laser is irradiated on the surface of the film layer, impurities in the film layer absorb heat to expand and start to move, and the absorbed heat and generated thermal stress can be dissipated through movement due to the fact that enough space is reserved around the impurities, so that the damage threshold of the film layer is improved, and good laser damage resistance is shown.
The features and properties of the present application are described in further detail below with reference to examples.
Example 1
This example provides an LBO crystal coated device, which is mainly prepared by the following steps:
1) preparation of polymethylsiloxanes
1783g of Methyltriethoxysilane (MTES), 266.8g of absolute ethanol and 586.8g of deionized water were added to the reactor, respectively, heated to 80 ℃ and when the liquid in the reactor began to boil, a mixture of 198g of deionized water and 184g of ethanol was added. Refluxing for 20h, and beginning to distill ethanol in the reactor, so that the final mass fraction of the polymethylsiloxane is about 33%, and obtaining the polymethylsiloxane.
The polymethylsiloxane was subjected to a freeze-drying treatment, and the molecular weight of the organopolysiloxane was measured by Gel Permeation Chromatography (GPC), with the weight average molecular weight Mw of 6130, as shown in fig. 1. The nuclear magnetic diagram of the polymethylsiloxane is shown in FIG. 2. In FIG. 2, c represents a cyclic structure and l represents a linear structure.
2)SiO2Preparation of the Sol
208g of tetraethyl silicate, 1084g of absolute ethanol and 37.4g of 35% aqueous ammonia were added to the reaction flask, and the mixture was stirred for 6 hours. Sealing and aging for 18 days, and performing reflux under reduced pressure for more than 10h after aging to remove ammonia to obtain SiO2And (3) sol.
3) Preparation of the first Sol
Adding 1000mL of polymethylsiloxane, 1000mL of n-butanol and 5000mL of absolute ethyl alcohol into a 10L reaction bottle, and stirring for more than 8 hours; adding 3000mL of SiO obtained in step 2)2And (3) sol. The finished sol was compounded and filtered through a 0.2 μm pore size filter to give a first sol.
By controlling the orientation of nano-scale low-refractive-index SiO in a 10L reaction bottle2The addition amount of the sol is adjusted to finally match the refractive index of the film sol. When the addition amount is 3000mL, the refractive index of the matching film reaches 1.4188, and the design requirement is met. The finished sol was compounded and filtered through a 0.2 μm pore size filter to give a first sol.
4) Preparation of the second Sol
208g of tetraethyl silicate, 1610g of absolute ethanol and 51.4g of 30% aqueous ammonia were added to the reaction flask, and the mixture was stirred for 3 hours. Sealing and aging for 5 days, and refluxing under reduced pressure for more than 10h after aging to remove ammonia to obtain SiO with solid content of about 3.3%2The refractive index of the anti-reflection film is about 1.1854, and before the sol is used, a filter element with the aperture of 0.2 mu m is used for filtering to obtain a second sol.
5) Preparation of the film systems
1 LBO crystal with the caliber of 120mm multiplied by 110mm multiplied by 10mm is manually cleaned by respectively using n-butyl alcohol and toluene, and then the LBO crystal is dried in a drying cabinet for more than 8 hours after being cleaned.
Changing the pulling speed of the first sol to ensure that the final film forming thickness is about 113.2 nm; the components were worked up for 24h at 140 ℃.
The pulling rate of the second sol was adjusted so that the thickness of the anti-reflection film was about 134.3 nm. The LBO crystal subjected to the preparation of the antireflection film is subjected to heat treatment at 160 ℃ for 24 hours.
The obtained LBO crystal coated member is shown in fig. 3, and fig. 3 shows an appearance of the LBO crystal coated member.
AFM photographs of the matching film and the antireflective film are shown in FIGS. 4 and 5, respectively, and it can be seen from FIGS. 4 and 5 that the matching film is an inorganic nano-structured SiO film due to the introduction of the organo-methicone2The particles are arranged more orderly and densely, the film-forming property of the surface of the particles is obviously improved, and the film layer is more compact and flat (Rq is 1.217 nm). The surface of the antireflection film obviously shows a disordered porous structure, the surface roughness is high (Rq is 9.735nm), and the porous structure enables the antireflection film to have a low refractive index and simultaneously improves the laser damage resistance threshold of the LBO crystal element.
Test example 1
The transmittance of the LBO crystal coated film element provided in example 1 was measured by a spectrophotometer, and the measurement results are shown in fig. 6. FIG. 6 shows the actually measured overall transmittance curve and the design curve of the LBO crystal coating element, and it can be seen from FIG. 6 that the transmittance of the film layer in the 527nm wave band reaches above 99.5%, and the transmittance in the (800 + -50) nm broadband anti-reflection interval is more than 99%, which meets the design requirement; even in the whole broadband range of 450 nm-1100 nm, the lowest value of the overall transmissivity of the LBO crystal element is close to 99 percent, and the preparation of the broadband antireflection film on the surface of the intense laser crystal element is really realized.
LBO crystal elements have been found to have slightly lower transmission than theoretical (difference < 0.35%), presumably due to intrinsic small absorption by the crystal material or diffuse reflection at the substrate-film interface.
Microscopic observation of the LBO crystal coated member provided in example 1 revealed that no film cracking occurred after 2 times of long-time high-temperature heat treatment (140 ℃ and 160 ℃), which fully demonstrated that the LBO crystal coated member provided in example 1 had excellent film physical and chemical properties.
Test example 2
Adopting an R-on-1 threshold test method, testing the laser wavelength to be 532nm, and carrying out damage test on the LBO crystal element prepared by the double-layer film, wherein the damage threshold of the LBO crystal element is more than 57J/cm2(532nm, 3ns), the damage threshold is far higher than that of other crystalsThe threshold of the element.
In conclusion, it can be seen that: the LBO crystal coating film component provided by the embodiment has the transmittance of more than 99.5 percent at a single wavelength of 527nm and the transmittance of more than 99 percent in a broadband interval of (800 +/-50) nm, and even in a wider wavelength range (450nm to 1100nm), the lowest overall transmittance of the component is still close to 99 percent. Due to the high intrinsic damage threshold of the LBO crystal element and the loose porous structure of the chemical film, the LBO crystal element prepared by the finished film layer shows a high damage threshold. No film cracking occurs during high-temperature heat treatment.
Comparative example 1
The present comparative example provides an LBO crystal coated member which is mainly produced by the following method:
1) preparation of the second Sol
208g of purified tetraethyl orthosilicate, 1610g of absolute ethanol and 51.4g of 30% ammonia water were added to a reaction flask, and stirred at 6 ℃ for 3 hours. Sealing and aging for 3-5 days, decompressing and refluxing for more than 10 hours after aging is finished, removing ammonia, and obtaining SiO with solid content of about 3.3 percent2The refractive index of the anti-reflection film is about 1.1854, and before the sol is used, a filter element with the aperture of 0.2 mu m is used for filtering to obtain a second sol.
2) Preparation of the film systems
1 LBO crystal with the caliber of 120mm multiplied by 110mm multiplied by 10mm is manually cleaned by respectively using n-butyl alcohol and toluene, and then the LBO crystal is dried in a drying cabinet for more than 8 hours after being cleaned.
The pulling rate of the second sol was adjusted so that the thickness of the anti-reflection film was about 134.3 nm. The LBO crystal subjected to the preparation of the antireflection film is subjected to heat treatment at 160 ℃ for 24 hours.
The obtained LBO crystal coated member is shown in fig. 7, and fig. 7 shows an appearance of the LBO crystal coated member of comparative example 1. Referring to fig. 7, it can be seen that the LBO crystal coated device provided by the present comparative example exhibited film cracking.
The above description is only a preferred embodiment of the present application and is not intended to limit the present application, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present application shall be included in the protection scope of the present application.
Claims (14)
1. A crystal coating film element, characterized by comprising:
a crystal substrate;
a matching film covered on the crystal substrate, wherein the matching film is made of polymethyl siloxane and SiO2A mixture of (a); and
the anti-reflection film covers the matching film, and the material of the anti-reflection film comprises SiO2；
Wherein the weight average molecular weight of the polymethylsiloxane is 8000 of 5000-;
the crystal coating element further comprises at least one buffer film positioned between the matching film and the antireflection film; the buffer film is made of polymethyl siloxane and SiO2A mixture of (a); the refractive indexes of the buffer film and the matching film are different; the refractive indexes of the buffer films of all layers are not completely the same; the crystal coating element comprises a plurality of layers of the antireflection films, and the refractive indexes of the antireflection films are not identical;
the film thickness of the matching film is 110-120nm, and the refractive index of the matching film is 1.35-1.44; the film thickness of the antireflection film is 130-137nm, and the refractive index of the antireflection film is 1.12-1.25.
2. The crystal film element of claim 1, wherein the material of the crystal substrate is lithium triborate crystal, β -phase barium metaborate crystal, or potassium dihydrogen phosphate crystal.
3. The crystal coated element according to claim 1 or 2, wherein the film thickness of the matching film is 113.2nm, and the refractive index of the matching film is 1.42; the film thickness of the antireflection film is 134.3nm, and the refractive index of the antireflection film is 1.19.
4. A preparation method of a crystal coated membrane element is characterized by comprising the following steps:
mixing the mixture containing polymethylsiloxane and SiO2The first sol is solidified to obtain a matching film after forming a film on the surface of a crystal substrate;
then will contain SiO2The second sol is solidified to obtain the anti-reflection film after forming a film on the surface of the matching film;
wherein the weight average molecular weight of the polymethylsiloxane is 8000 of 5000-; the film thickness of the matching film is 110-120nm, and the refractive index of the matching film is 1.35-1.44; the film thickness of the antireflection film is 130-137nm, and the refractive index of the antireflection film is 1.12-1.25.
5. The method for producing a crystal coated member according to claim 4, further comprising, after forming the matching film and before forming the antireflection film: forming at least one layer of buffer film on the surface of the matching film;
wherein the preparation step of the buffer film comprises the following steps: mixing the mixture containing polymethylsiloxane and SiO2And curing the third sol to obtain the buffer film.
6. The method for producing a crystal coated member according to claim 5,
the polymethylsiloxane and the SiO in the first sol and the third sol2Are different.
7. The method for producing a crystal coated member according to claim 5, wherein the polymethylsiloxane and the SiO are contained in a third sol used for producing each of the buffer films2Are different.
8. The method for producing a crystal coated element according to claim 4, wherein the film thickness of the matching film is 113.2nm, and the refractive index of the matching film is 1.42; the film thickness of the antireflection film is 134.3nm, and the refractive index of the antireflection film is 1.19.
9. The method for producing a crystal coated member according to claim 4,
SiO in the first sol2The particle size of the (B) is 55nm to 78nm, and the viscosity is 1.82cp to 1.98 cp.
10. The method for producing a crystal coated element according to claim 4, wherein SiO in the second sol2The particle size of the (B) is 55-70 nm, and the viscosity is 1.64-1.69 cp.
11. The method for producing a crystal coated element according to claim 4, wherein the polymethylsiloxane and SiO in the first sol2The mass ratio of (1) to (0.1-2).
12. The method for producing a crystal coated member according to any one of claims 4 to 11, wherein the polymethylsiloxane is produced by:
heating the mixture of methyltriethoxysilane, anhydrous ethanol and water to 75-85 deg.C, adding 45-50 wt% ethanol water solution when the liquid begins to boil, mixing, refluxing for 15-25h, and removing ethanol.
13. A crystal film system, comprising:
the matching film is made of polymethyl siloxane and SiO2A mixture of (a); and
the anti-reflection film covers the surface of the matching film, and the material of the anti-reflection film comprises SiO2；
Wherein the weight average molecular weight of the polymethylsiloxane is 8000 of 5000-;
the film thickness of the matching film is 110-120nm, and the refractive index of the matching film is 1.35-1.44; the film thickness of the antireflection film is 130-137nm, and the refractive index of the antireflection film is 1.12-1.25.
14. The crystal film system of claim 13, further comprising a buffer film, wherein the buffer filmThe buffer film is positioned between the anti-reflection film and the matching film, and the buffer film is made of polymethyl siloxane and SiO2A mixture of (a).
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| CN103757706A (en) * | 2014-01-08 | 2014-04-30 | 同济大学 | Preparation method of nonlinear optical crystal surface antireflection protective film |
| CN106435487A (en) * | 2016-10-10 | 2017-02-22 | 同济大学 | Preparation method of lithium triborate crystal high-laser-damaged-threshold antireflection film |
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| CN103757706A (en) * | 2014-01-08 | 2014-04-30 | 同济大学 | Preparation method of nonlinear optical crystal surface antireflection protective film |
| CN106435487A (en) * | 2016-10-10 | 2017-02-22 | 同济大学 | Preparation method of lithium triborate crystal high-laser-damaged-threshold antireflection film |
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