CN111856628A - Anti-reflection film for sapphire substrate and preparation method thereof - Google Patents

Anti-reflection film for sapphire substrate and preparation method thereof Download PDF

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CN111856628A
CN111856628A CN202010731907.0A CN202010731907A CN111856628A CN 111856628 A CN111856628 A CN 111856628A CN 202010731907 A CN202010731907 A CN 202010731907A CN 111856628 A CN111856628 A CN 111856628A
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sio
film layer
thin film
oxygen
nitrogen
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徐照英
刘垚
王锦标
苏永要
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Chongqing University of Arts and Sciences
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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/11—Anti-reflection coatings
    • G02B1/113—Anti-reflection coatings using inorganic layer materials only
    • G02B1/115—Multilayers
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/0021—Reactive sputtering or evaporation
    • C23C14/0036—Reactive sputtering
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/0021—Reactive sputtering or evaporation
    • C23C14/0036—Reactive sputtering
    • C23C14/0084—Producing gradient compositions
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/10—Glass or silica
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering

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Abstract

The invention provides an anti-reflection film for a sapphire substrate, which comprises five film layers, wherein SiO is sequentially arranged from a sapphire material basal plane (1) to the outside2A thin film layer (2) and a first SiOxNyA thin film layer (3) and second SiOxNyA thin film layer (4) and a third SiOxNyA thin film layer (5) and fourth SiOxNyA film layer (6); the anti-reflection film is used for preparing SiO by a balanced magnetron sputtering method2A film layer (2) and SiO prepared by sequentially decreasing the atomic percent of nitrogen and increasing the atomic percent of oxygen through different rates of nitrogen, oxygen and argonxNyA thin film layer. The anti-reflection film effectively improves the transmittance of the sapphire material in an infrared band and reduces the reflectivity of the sapphire material, so that the sapphire material has small absorption and scattering properties; meanwhile, the anti-reflection film is high in bonding strength with a sapphire substrate, high in density and firm in bonding, can be effectively used in high-strength fields such as military photoelectric equipment and is long in service life.

Description

Anti-reflection film for sapphire substrate and preparation method thereof
Technical Field
The invention relates to the technical field of optical films, in particular to an anti-reflection film for a sapphire substrate and a preparation method thereof.
Background
Sapphire crystal-the hardest oxide crystal, is alumina (Al)2O3) Most basic single crystal morphology. The sapphire optical material is widely applied to military technical fields such as submarine photoelectric masts, land-based photoelectric countermeasures, airborne photoelectric pods, large-scale transport machine visible windows, missile hoods and the like due to excellent physical properties (high hardness, high bending strength, wind and sand resistance, high temperature resistance, corrosion resistance, good optical properties, excellent electrical insulation performance and the like), and is a window material, a high-quality optical material, a wear-resistant bearing material and a substrate material of infrared devices, missiles, submarines, satellite space technologies, detection, high-power strong laser and the like.
However, sapphire still encounters some technical difficulties in practical application, for example, sapphire material shows different degrees of lattice vibration absorption above the 4.0 μm band of the medium wave, and the reduction amplitude and thickness are obviously related, which limits the application of sapphire in the infrared band to some extent. The antireflection film, also called as an antireflection film, has the main function of reducing or eliminating the reflected light from optical surfaces such as lenses, prisms, plane mirrors and the like, thereby increasing the light transmission of the elements and reducing or eliminating the stray light of the system. The prior art generally eliminates the limitation on the infrared band by preparing an antireflection film on the surface of sapphire to reduce the reflectivity and increase the transmittance of the sapphire.
However, the sapphire material used as the multispectral hard protection window not only requires good optical performance, but also needs a compact, firm and wear-resistant film layer to meet the actual application requirements of military optoelectronic equipment; however, in the prior art, due to the transverse accumulation of internal stress and the corrosion of external severe temperature impact and high-humidity and high-salt environment, the anti-reflection and anti-reflection film for the sapphire substrate often causes the effective service life of the film layer to be obviously reduced, the bonding strength between the film layer and the sapphire substrate to be reduced, the structural stability of the film layer to be poor, and even the film layer to have the phenomena of corrosion spot, cracking, falling off and the like.
Disclosure of Invention
In view of the problems in the prior art, an object of the present invention is to provide an anti-reflection film for a sapphire substrate, which utilizes the principle that the refractive index changes continuously, so as to improve the transmittance of the infrared band and reduce the reflectance thereof, so that the sapphire material has small absorption and scattering properties as a whole; meanwhile, the anti-reflection film has high bonding strength with the sapphire substrate and high density, can effectively avoid temperature impact and corrosion in a high-humidity high-salt environment, and avoids the phenomena of film falling and cracking.
The invention also aims to provide a preparation method of the anti-reflection film for the sapphire substrate.
The purpose of the invention is realized by the following technical scheme:
an antireflection film for a sapphire substrate, characterized in that: the antireflection film comprises five film layers; the five thin film layers are sequentially SiO from the sapphire material base surface to the outside2Thin film layer, first SiOxNyThin film layer, second SiOxNyThin film layer, third SiOxNyThin film layer, fourth SiOxNyA thin film layer; wherein the first SiOxNyThin film layer to fourth SiOxNyThe atomic percent of nitrogen elements in the thin film layer is sequentially decreased and the atomic percent of oxygen elements in the thin film layer is sequentially increased, and the atomic percent of the nitrogen elements is not more than 40at.%, and the atomic percent of the oxygen elements is not more than 60 at.%.
For further optimization, the SiO2The thickness of the thin film layer is 130-170 nm.
For further optimization, the first SiOxNyThin film layer, second SiOxNyThin film layer, third SiOxNyThin film layer, fourth SiOxNyThe thickness of the thin film layer is 10-30 nm, 40-85 nm, 90-140 nm and 146-200 nm respectively.
For further optimization, the first SiOxNyThe atomic percent of nitrogen element and the atomic percent of oxygen element in the film layer are respectively 38-40 at.% and 13-15 at.%; the second SiOxNyThe atomic percent of nitrogen element and the atomic percent of oxygen element in the film layer are respectively 28-30 at.% and 28-30 at.%; the third SiOxNyThe atomic percent of nitrogen element and oxygen element of the thin film layer are respectively 18-20 at.% and 43-45 at.%; the fourth SiOxNyThe atomic percent of nitrogen element and the atomic percent of oxygen element in the film layer are respectively 8-10 at.% and 58-60 at.%.
The silicon dioxide has the characteristics of high melting point, firm film layer, wear resistance, corrosion resistance, strong protective capability, less scattering and absorption of light and the like, and the bonding strength of the film layer and the substrate is increased by preparing the silicon dioxide film layer on the sapphire substrate, so that the film layer is prevented from falling off from the substrate.
SiOxNyThe refractive index of the film is gradually reduced along with the increase of the content of the oxygen element, and the refractive index is gradually reduced along with the reduction of the content of the nitrogen element; the invention uses multilayer SiO with refractive index gradually reduced from inner layer to outer layerxNyThin film layer matching SiO2The film layer enables the refractive index to continuously change along the normal direction of the surface of the film layer and keeps unchanged in the direction parallel to the film surface, so that the transmittance of an infrared band is improved, the reflectivity of the infrared band is reduced, and the whole sapphire material has smaller absorption and scattering characteristics. Meanwhile, the total content of oxygen and nitrogen is increased, so that the SiO from inside to outsidexNyThe content of silicon element in the thin film layer is gradually reduced, thereby leading to the reduction of Si-Si bonds and the increase of Si-N and Si-O, and further leading to SiOxNyThe film layer is more stable and compact from inside to outside, the bonding strength and stability of the film are further ensured, and the abrasion resistance of the film is improved.
A preparation method of an anti-reflection film for a sapphire substrate is characterized by comprising the following steps: firstly, cleaning a sapphire material and a target material to remove surface impurities; then SiO is carried out by adopting non-equilibrium magnetron sputtering equipment2Deposition and introduction of thin film layerThe gas source is oxygen and argon; redepositing SiOxNyThe thin film layer is filled with argon, oxygen and nitrogen as gas sources, and the first SiO is deposited in sequence by adjusting the gas flow rate of the nitrogen, the oxygen and the argonxNyThin film layer, second SiOxNyThin film layer, third SiOxNyThin film layer and fourth SiOxNyA thin film layer; and obtaining the anti-reflection film.
Further optimization, the specific steps of the cleaning are as follows: firstly, cleaning a sapphire material by adopting absolute ethyl alcohol, then placing the cleaned sapphire material on a sample table of a vacuum chamber of non-equilibrium magnetron sputtering equipment, and taking silicon (99.99%) as a target material; the vacuum chamber was closed and evacuated to 3.0x10-3After Pa, turning on a bias power supply, applying 750-850V direct current voltage and 90-110V bias voltage on the sapphire material, opening an air valve, continuously introducing argon gas, enabling the flow of the argon gas to be 45-55 sccm, cleaning the sapphire material for 18-22 min, and then turning off the power supply; and then turning on a target power supply, applying a current of 0.5A to carry out pre-sputtering cleaning on the target for 9-11 min, and removing surface impurities.
For further optimization, the SiO2The deposition of the thin film layer is specifically as follows: after cleaning the substrate material, introducing oxygen, wherein the introduction amount of the oxygen is 55-65 sccm, then introducing argon, adjusting the deposition temperature to be 170-190 ℃ by using a heating device and using a high-purity Si (99.99%) target as a cathode when the air pressure of a vacuum chamber rises to 1.0-1.5 Pa, adjusting the negative bias to be 48-52V, turning on a target sputtering power supply, setting the current to be 0.6-0.8A, and depositing for 35-45 min.
For further optimization, the SiOxNyThe deposition of the thin film layer is specifically as follows: adjusting the pressure of an unbalanced magnetron sputtering device to be 5x10-3Pa, introducing nitrogen, oxygen and argon; when the air pressure of a vacuum chamber rises to 1.0-1.5 Pa, taking a high-purity Si (99.99%) target as a cathode, adjusting the deposition temperature to 170-190 ℃ through a heating device, adjusting the negative bias to 48-52V, turning on a target sputtering power supply, and setting the current to 0.6-0.8A; by controlling the flow rate of nitrogen, oxygen and argon, SiO with different nitrogen content and oxygen content is depositedxNyA thin film layer.
For further optimization, the first SiOxNyThe flow rates of the nitrogen, the oxygen and the argon of the thin film layer are respectively 78-82 sccm, 8-12 sccm and 83-87 sccm, and the deposition time is 5-7 min.
For further optimization, the second SiOxNyThe flow rates of nitrogen, oxygen and argon of the thin film layer are respectively 68-72 sccm, 20-24 sccm and 83-87 sccm, and the deposition time is 14-18 min.
For further optimization, the third SiOxNyThe flow rates of the nitrogen, the oxygen and the argon of the thin film layer are respectively 58-62 sccm, 33-37 sccm and 83-87 sccm, and the deposition time is 28-34 min.
For further optimization, the fourth SiOxNyThe flow rates of nitrogen, oxygen and argon of the thin film layer are 8-12 sccm, 58-62 sccm and 83-87 sccm respectively, and the deposition time is 40-52 min.
The invention has the following technical effects:
the invention uses SiO2The film layer and four layers of SiO with the atom percent of nitrogen decreasing and the atom percent of oxygen increasing sequentiallyxNyThe composite anti-reflection film composed of the thin film layer enables the refractive index to continuously change along the normal direction of the surface of the film layer and keeps unchanged in the direction parallel to the film surface, so that the transmittance of an infrared band is effectively improved, the reflectivity of the infrared band is reduced, and the whole sapphire material has smaller absorption and scattering characteristics. At the same time, by SiO2The inherent characteristics of the thin film layer improve the bonding strength between the thin film and the substrate and reduce the internal stress between the thin film and the substrate; four-layer SiO by gradient change of atomic percent of nitrogen element and oxygen elementxNyThe thin film layer, thereby reduce the internal stress between thin film layer and the thin film layer, improve the bonding strength between thin film layer and the thin film layer. And, four layers of SiOxNyThe oxygen element and the nitrogen element of the film layer are changed in percentage, so that the four film layers are more compact from inside to outside, the density of the antireflection film is increased, the stability and the firmness of the antireflection film are improved, and the antireflection film is ensured to be wear-resistant and resistantThe corrosion resistance is stronger, the service life of the film is prolonged, the application range of the film is enlarged, and the film can be applied to high-strength fields such as military photoelectric equipment and the like.
Drawings
FIG. 1 is a schematic view showing a structure of an antireflection film in an embodiment of the present invention.
Fig. 2 is a graph showing light transmittance of antireflection films before and after the coating of the sapphire material base surface in example 1 of the present invention.
Fig. 3 is a graph showing the reflectance of the antireflection film before and after the coating of the sapphire material base surface in example 1 of the present invention.
FIG. 4 is an electron microscope image of the sapphire material after being coated in example 2 of the present invention.
Fig. 5 is an SEM image of the sapphire material after being plated in example 2 of the present invention.
Wherein, 1, a sapphire material basal plane; 2. SiO 22A thin film layer; 3. first SiOxNyA thin film layer; 4. second SiOxNyA thin film layer; 5. third SiOxNyA thin film layer; 6. fourth SiOxNyA thin film layer.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1:
a preparation method of an anti-reflection film for a sapphire substrate is characterized by comprising the following steps:
a. firstly, cleaning a sapphire material and a target material to remove surface impurities, and specifically comprising the following steps: firstly, cleaning a sapphire material by adopting absolute ethyl alcohol, then placing the cleaned sapphire material on a sample table of a vacuum chamber of non-equilibrium magnetron sputtering equipment, and taking silicon (99.99%) as a target material; closing the vacuum chamber and vacuumizingEmpty to 3.0x10-3After Pa, a bias voltage power supply is turned on, 750V direct current voltage and 90V bias voltage are applied to the sapphire material, an air valve is opened, argon gas is continuously introduced, the flow of the argon gas is 45sccm, and the power supply is turned off after the sapphire material is cleaned for 18 min; then, a target power supply is turned on, and 0.5A of current is applied to carry out pre-sputtering cleaning on the target for 9min, so as to remove surface impurities.
b. After the substrate material is cleaned, SiO is carried out2Depositing the thin film layer 2, introducing oxygen with the oxygen introduction amount of 55sccm, then introducing argon with the argon introduction amount of 83sccm, adjusting the deposition temperature to 170 ℃ by using a heating device and adjusting the negative bias to 48V by using a high-purity Si (99.99%) target as a cathode when the air pressure of a vacuum chamber rises to 1.0Pa, turning on a target sputtering power supply, setting the current to 0.6A, and depositing for 35 min; complete the SiO2After the deposition of the thin film layer 2, the air valve is closed, the power supply is cut off, and the temperature is reduced to the normal temperature.
c. Then adjusting the pressure of the unbalanced magnetron sputtering equipment to be 5x10-3Pa, introducing nitrogen, oxygen and argon; when the air pressure of a vacuum chamber rises to 1.0Pa, a high-purity Si (99.99%) target is used as a cathode, the deposition temperature is adjusted to 170 ℃ through a heating device, the negative bias is adjusted to 48V, a target sputtering power supply is turned on, and the current is set to be 0.6A; controlling the flow rates of the nitrogen, the oxygen and the argon to be 78sccm, 8sccm and 83sccm respectively, and the deposition time to be 5min to complete the first SiOxNyDeposition of the thin film layer 3.
d. Keeping other parameters unchanged, changing the flow rates of the nitrogen and the oxygen into 68sccm and 20sccm, and depositing for 14min to complete the second SiOxNyDeposition of a thin film layer 4;
e. keeping other parameters unchanged, changing the flow rates of the nitrogen and the oxygen into 58sccm and 33sccm, and depositing for 28min to obtain the third SiOxNyDeposition of a thin film layer 5;
f. keeping other parameters unchanged, only changing the flow rates of the nitrogen and the oxygen into 8sccm and 58sccm, and depositing for 40min to complete the fourth SiOxNyDeposition of the thin film layer 6.
The final antireflection film comprises five layers of filmsLayer of SiO with the thickness of 130nm from the base surface 1 of the sapphire material to the outside in sequence2Film layer 2, first SiO with thickness of 10nmxNyFilm layer 3, second SiO with thickness of 40nmxNyThin film layer 4, third SiO with thickness of 90nmxNyFilm layer 5, fourth SiO with thickness of 146nmxNy A film layer 6.
Wherein the first SiOxNyThin film layer 3 to fourth SiOxNyThe atomic percent of nitrogen element in the film layer 6 is decreased gradually, the atomic percent of oxygen element is increased gradually, and the first SiOxNyThe atomic percent of nitrogen element and the atomic percent of oxygen element in the film layer 3 are respectively 38at.% and 13 at.%; second SiOxNyThe atomic percent of nitrogen element and the atomic percent of oxygen element in the thin film layer 4 are respectively 28at.% and 28 at.%; third SiOxNyThe atomic percent of nitrogen element and the atomic percent of oxygen element in the thin film layer 5 are respectively 18at.% and 43 at.%; fourth SiOxNyThe atomic percent of nitrogen element and the atomic percent of oxygen element in the thin film layer 6 were 8at.% and 58at.%, respectively.
Example 2:
a preparation method of an anti-reflection film for a sapphire substrate is characterized by comprising the following steps:
a. firstly, cleaning a sapphire material and a target material to remove surface impurities, and specifically comprising the following steps: firstly, cleaning a sapphire material by adopting absolute ethyl alcohol, then placing the cleaned sapphire material on a sample table of a vacuum chamber of non-equilibrium magnetron sputtering equipment, and taking silicon (99.99%) as a target material; the vacuum chamber was closed and evacuated to 3.0x10-3After Pa, a bias voltage power supply is turned on, 800V direct current voltage and 100V bias voltage are applied to the sapphire material, an air valve is opened, argon gas is continuously introduced, the flow of the argon gas is 50sccm, and the power supply is turned off after the sapphire material is cleaned for 20 min; then, a target power supply is turned on, and 0.5A of current is applied to carry out pre-sputtering cleaning on the target for 10min, so as to remove surface impurities.
b. After the substrate material is cleaned, SiO is carried out2Depositing the thin film layer 2, and introducing oxygen with the oxygen introduction amount of 60sccm, then introducing argon gas, wherein the introducing amount of the argon gas is 85sccm, when the air pressure of a vacuum chamber rises to 1.3Pa, taking a high-purity Si (99.99%) target as a cathode, adjusting the deposition temperature to 180 ℃ through a heating device, adjusting the negative bias to 50V, turning on a target sputtering power supply, setting the current to be 0.7A, and depositing for 40 min; complete the SiO2After the deposition of the thin film layer 2, the air valve is closed, the power supply is cut off, and the temperature is reduced to the normal temperature.
c. Then adjusting the pressure of the unbalanced magnetron sputtering equipment to be 5x10-3Pa, introducing nitrogen, oxygen and argon; when the air pressure of a vacuum chamber rises to 1.3Pa, a high-purity Si (99.99%) target is used as a cathode, the deposition temperature is adjusted to 180 ℃ through a heating device, the negative bias is adjusted to 50V, a target sputtering power supply is turned on, and the current is set to be 0.7A; the first SiO is finished by controlling the flow rates of nitrogen, oxygen and argon to be 80sccm, 10sccm and 85sccm respectively and the deposition time to be 6minxNyDeposition of the thin film layer 3.
d. Keeping other parameters unchanged, changing the flow of the nitrogen and the oxygen into 70sccm and 22sccm, and depositing for 16min to complete the second SiOxNyDeposition of a thin film layer 4;
e. keeping other parameters unchanged, changing the flow rates of the nitrogen and the oxygen into 60sccm and 35sccm, and depositing for 31min to obtain the third SiOxNyDeposition of a thin film layer 5;
f. keeping other parameters unchanged, changing the flow rates of the nitrogen and the oxygen into 10sccm and 60sccm, and depositing for 46min to obtain the fourth SiOxNyDeposition of the thin film layer 6.
The finally prepared antireflection film comprises five film layers which are sequentially SiO with the thickness of 150nm from the base surface 1 of the sapphire material to the outside2Film layer 2, first SiO with thickness of 20nmxNyFilm layer 3, second SiO with thickness of 57nmxNyThin film layer 4, third SiO with thickness of 115nmxNyFilm layer 5, fourth SiO with thickness 173nmxNy A film layer 6.
Wherein the first SiOxNyThin film layer 3 to fourth SiOxNyFilm layer 6The atomic percent of the middle nitrogen element is decreased gradually, the atomic percent of the oxygen element is increased gradually, and the first SiOxNyThe atomic percent of nitrogen element and the atomic percent of oxygen element in the film layer 3 are respectively 39at.% and 14 at.%; second SiOxNyThe atomic percent of nitrogen element and the atomic percent of oxygen element in the thin film layer 4 are respectively 29at.% and 29 at.%; third SiOxNyThe atomic percent of nitrogen element and the atomic percent of oxygen element in the thin film layer 5 are respectively 19at.% and 44 at.%; fourth SiOxNyThe atomic percent of nitrogen and the atomic percent of oxygen in the thin film layer 6 were 9at.% and 59 at.%.
Example 3:
a preparation method of an anti-reflection film for a sapphire substrate is characterized by comprising the following steps:
a. firstly, cleaning a sapphire material and a target material to remove surface impurities, and specifically comprising the following steps: firstly, cleaning a sapphire material by adopting absolute ethyl alcohol, then placing the cleaned sapphire material on a sample table of a vacuum chamber of non-equilibrium magnetron sputtering equipment, and taking silicon (99.99%) as a target material; the vacuum chamber was closed and evacuated to 3.0x10-3After Pa, turning on a bias power supply, applying 850V direct current voltage and 110V bias voltage on the sapphire material, opening an air valve, continuously introducing argon gas with the flow of 55sccm, cleaning the sapphire material for 22min, and then turning off the power supply; then, a target power supply is turned on, and 0.5A of current is applied to carry out pre-sputtering cleaning on the target for 11min, so as to remove surface impurities.
b. After the substrate material is cleaned, SiO is carried out2Depositing the thin film layer 2, introducing oxygen with the introduction amount of 65sccm, then introducing argon with the introduction amount of 87sccm, adjusting the deposition temperature to 190 ℃ by using a heating device and adjusting the negative bias to 52V by using a high-purity Si (99.99%) target as a cathode when the air pressure of a vacuum chamber rises to 1.5Pa, turning on a target sputtering power supply, setting the current to 0.8A, and depositing for 45 min; complete the SiO2After the deposition of the thin film layer 2, the air valve is closed, the power supply is cut off, and the temperature is reduced to the normal temperature.
c. Then adjusting the pressure of the unbalanced magnetron sputtering equipment to be 5x10-3Pa, introduction of nitrogenGas, oxygen and argon; when the air pressure of a vacuum chamber rises to 1.5Pa, a high-purity Si (99.99%) target is used as a cathode, the deposition temperature is adjusted to 190 ℃ through a heating device, the negative bias is adjusted to 52V, a target sputtering power supply is turned on, and the set current is 0.8A; the first SiO is finished by controlling the flow rates of the nitrogen, the oxygen and the argon to be 82sccm, 12sccm and 87sccm respectively and the deposition time to be 7minxNyDeposition of the thin film layer 3.
d. Keeping other parameters unchanged, changing the flow rates of the nitrogen and the oxygen into 72sccm and 24sccm, and depositing for 18min to complete the second SiOxNyDeposition of a thin film layer 4;
e. keeping other parameters unchanged, changing the flow rates of the nitrogen and the oxygen into 62sccm and 37sccm, and depositing for 34min to complete the third SiOxNyDeposition of a thin film layer 5;
f. keeping other parameters unchanged, changing the flow rates of the nitrogen and the oxygen into 12sccm and 62sccm, and depositing for 52min to complete the fourth SiOxNyDeposition of the thin film layer 6.
The finally prepared antireflection film comprises five film layers which are sequentially SiO with the thickness of 170nm from the base surface 1 of the sapphire material to the outside2Film layer 2, first SiO with thickness of 30nmxNyFilm layer 3, second SiO with thickness of 85nmxNyFilm layer 4, third SiO with thickness of 140nmxNyFilm layer 5, fourth SiO with thickness of 200nmxNy A film layer 6.
Wherein the first SiOxNyThin film layer 3 to fourth SiOxNyThe atomic percent of nitrogen element in the film layer 6 is decreased gradually, the atomic percent of oxygen element is increased gradually, and the first SiOxNyThe atomic percent of nitrogen element and the atomic percent of oxygen element in the film layer 3 are respectively 40at.% and 15 at.%; second SiOxNyThe atomic percent of nitrogen element and the atomic percent of oxygen element in the thin film layer 4 are respectively 30at.% and 30 at.%; third SiOxNyThe atomic percent of nitrogen element and the atomic percent of oxygen element in the thin film layer 5 are respectively 20at.% and 45 at.%; fourth SiOxNyThe atomic percent of nitrogen element and the atomic percent of oxygen element in the thin film layer 6 were 10at.% and 60 at.%.
FIG. 2 is a graph showing the transmittance of sapphire before and after plating an antireflection film according to example 1 of the present invention on the same sapphire substrate; FIG. 3 is a graph showing the reflectance of sapphire on the same sapphire substrate before and after plating an antireflection film according to example 1 of the present invention. It can be seen that the light average transmittance of the anti-reflection film prepared by the invention is higher than 97%, and compared with that before film plating, the transmittance is improved by about 13%; meanwhile, the reflectivity of the sapphire substrate before being coated with the film is about 7.5%, the light reflection loss is very large, and the reflectivity of the anti-reflection film is reduced to a level less than 1.5% after the anti-reflection film is prepared, so that the reflectivity is obviously reduced.
The bonding force of the antireflection film in example 2 of the present invention was evaluated by a nano scratch method, and the indenter was a diamond indenter having a diameter of 5um, the load was increased from 0mN to 100mN, and the scratch length was 1 mm. Meanwhile, as shown in the scanning electron microscope result of fig. 4, the bonding force between the film and the substrate is good, cracks are almost not generated in the overall observation, and the film peeling phenomenon is not generated. As can be seen from FIG. 5, the antireflection film prepared by the method has the advantages of smooth and uniform surface, high density, firm bonding and high stability; which proves effective in resisting wear and corrosion.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.

Claims (7)

1. An antireflection film for a sapphire substrate, characterized in that: the antireflection film comprises five film layers; the five thin film layers are sequentially SiO from the sapphire material base surface (1) to the outside2A thin film layer (2) and a first SiOxNyFilm layer (3), secondSiO 2xNyA thin film layer (4) and a third SiOxNyA thin film layer (5) and fourth SiOxNyA film layer (6); wherein the first SiOxNyThin film layer (3) to fourth SiOxNyThe atomic percentages of nitrogen and oxygen in the thin film layer (6) are sequentially decreased and increased, and the atomic percentages of nitrogen and oxygen should be no more than 40at.% and 60at.%, respectively.
2. An antireflection film for a sapphire substrate according to claim 1, wherein: the SiO2The thickness of the thin film layer (2) can be 130-170 nm.
3. An antireflection film for a sapphire substrate according to claim 1, wherein: the first SiOxNyA thin film layer (3) and second SiOxNyA thin film layer (4) and a third SiOxNyA thin film layer (5) and fourth SiOxNyThe thickness of the thin film layer (6) can be 10-30 nm, 40-85 nm, 90-140 nm and 146-200 nm respectively.
4. The method for preparing an antireflection film for a sapphire substrate according to claim 1, wherein the method comprises the following steps: firstly, cleaning a sapphire material and a target material to remove surface impurities; then SiO is carried out by adopting non-equilibrium magnetron sputtering equipment2Depositing the thin film layer (2), and introducing oxygen and argon into a gas source; redepositing SiOxNyThe thin film layer is filled with argon, oxygen and nitrogen as gas sources, and the first SiO is deposited in sequence by adjusting the gas flow rate of the nitrogen, the oxygen and the argonxNyA thin film layer (3) and second SiOxNyA thin film layer (4) and a third SiOxNyThin film layer (5) and fourth SiOxNyA film layer (6); and obtaining the anti-reflection film.
5. According toThe method for preparing an antireflection film for a sapphire substrate according to claim 4, wherein the method comprises the following steps: the specific steps of the cleaning are as follows: firstly, cleaning a sapphire material by adopting absolute ethyl alcohol, then placing the cleaned sapphire material on a sample table of a vacuum chamber of non-equilibrium magnetron sputtering equipment, and taking silicon (99.99%) as a target material; the vacuum chamber was closed and evacuated to 3.0x10-3After Pa, turning on a bias power supply, applying 750-850V direct current voltage and 90-110V bias voltage on the sapphire material, opening an air valve, continuously introducing argon gas, enabling the flow of the argon gas to be 45-55 sccm, cleaning the sapphire material for 18-22 min, and then turning off the power supply; and then turning on a target power supply, applying a current of 0.5A to carry out pre-sputtering cleaning on the target for 9-11 min, and removing surface impurities.
6. The method for preparing an antireflection film for a sapphire substrate according to claim 4, wherein the method comprises the following steps: the SiO2The deposition of the thin film layer (2) is specifically as follows: after cleaning the substrate material, introducing oxygen, wherein the introduction amount of the oxygen is 55-65 sccm, then introducing argon, adjusting the deposition temperature to be 170-190 ℃ by using a heating device and using a high-purity Si (99.99%) target as a cathode when the air pressure of a vacuum chamber rises to 1.0-1.5 Pa, adjusting the negative bias to be 48-52V, turning on a target sputtering power supply, setting the current to be 0.6-0.8A, and depositing for 35-45 min.
7. The method for preparing an antireflection film for a sapphire substrate according to claim 4, wherein the method comprises the following steps: the SiOxNyThe deposition of the thin film layer is specifically as follows: adjusting the pressure of an unbalanced magnetron sputtering device to be 5x10-3Pa, introducing nitrogen, oxygen and argon; when the air pressure of a vacuum chamber rises to 1.0-1.5 Pa, taking a high-purity Si (99.99%) target as a cathode, adjusting the deposition temperature to 170-190 ℃ through a heating device, adjusting the negative bias to 48-52V, turning on a target sputtering power supply, and setting the current to 0.6-0.8A; by controlling the flow rate of nitrogen, oxygen and argon, SiO with different nitrogen content and oxygen content is depositedxNyA thin film layer.
CN202010731907.0A 2020-07-27 2020-07-27 Anti-reflection film for sapphire substrate and preparation method thereof Withdrawn CN111856628A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112698430A (en) * 2020-12-11 2021-04-23 中材人工晶体研究院有限公司 ZnS substrate long-wave infrared anti-reflection protective film and preparation method thereof
CN112877642A (en) * 2021-04-29 2021-06-01 蓝思科技（长沙）有限公司 Anti-fingerprint film, glass product and preparation method thereof

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112698430A (en) * 2020-12-11 2021-04-23 中材人工晶体研究院有限公司 ZnS substrate long-wave infrared anti-reflection protective film and preparation method thereof
US12032122B2 (en) 2020-12-11 2024-07-09 Sinoma Synthetic Crystals Co., Ltd. Long-wave infrared anti-reflection protective film on ZnS substrate and preparation method thereof
CN112877642A (en) * 2021-04-29 2021-06-01 蓝思科技（长沙）有限公司 Anti-fingerprint film, glass product and preparation method thereof

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