CN116970928A - Preparation method of optical antireflection film - Google Patents

Abstract

The invention provides a preparation method of an optical antireflection film, which comprises the following steps: providing a substrate layer; recycling an antireflection film sub-film layer on one side surface of the substrate layer; the antireflection film sub-film layer comprises: forming a first film by using an atomic layer deposition mode; forming a second film on the side of the first film away from the substrate layer by using an atomic layer deposition mode and at the same temperature as the first film; the crystallization temperature of the second film is greater than the crystallization temperature of the first film; cycling the antireflection film sub-film layer for N times, wherein the first film is formed on one side surface of the second film formed in the previous cycle, which is away from the substrate layer; after the circulation of the antireflection film sub-film layer is finished, a first film is formed on the surface of one side of the second film farthest from the substrate layer, which is away from the substrate layer. The preparation method of the optical antireflection film provided by the invention can improve the light transmittance of the antireflection film.

Description

A method for preparing optical anti-reflection coating

Technical field

The invention relates to the field of thin film technology, and in particular to a method for preparing an optical anti-reflection film.

Background technique

Antireflection coating is the most widely used and most produced optical film. Its main function is to reduce or eliminate the reflected light on the surfaces of optical devices such as lenses, prisms, and plane mirrors, thereby increasing the light transmission of these components and reducing or eliminating system Stray light, so the important characteristic index of the anti-reflection coating is the light transmittance. Grains refer to small, irregular-shaped crystals that make up polycrystals. Grain size refers to the number of grains per unit volume (or unit area) or the average line length (or diameter) of the grains. The degree of crystallization of the film layer is one of the key factors that affects the optical performance of the antireflection coating. For example, a film layer with a high degree of crystallinity will cause light to be scattered and absorbed by the crystal grains during the transmission process of the film layer, reducing the light transmittance and affecting the optical performance. . The key factors that affect the crystallization degree and grain size of the antireflection coating include: antireflection coating material, antireflection coating thickness, etc.

Atomic layer deposition (ALD) is a method of plating layer by layer on the surface of a substrate layer in the form of a nearly single-atom film. Therefore, Atomic layer deposition technology has obvious advantages in controlling the thickness of the anti-reflection coating. However, when the thickness of the anti-reflection coating reaches a certain level, due to the influence of the material characteristics of the anti-reflection coating itself, the degree of crystallization of the anti-reflection coating is high, which increases the probability of light being scattered by the crystal grains during transmission, resulting in the anti-reflection coating. The light transmittance is low.

Contents of the invention

Therefore, the technical problem to be solved by the present invention is to overcome the shortcoming of low light transmittance of the anti-reflection film in the prior art, thereby providing a method for preparing an optical anti-reflection film.

The invention provides a method for preparing an optical anti-reflection film, which includes: providing a substrate layer; performing anti-reflection film sub-layer circulation on one side of the substrate layer; the anti-reflection film sub-layer includes: using an atomic layer The first film is formed by deposition; the second film is formed on the side of the first film away from the substrate layer using atomic layer deposition and at the same temperature as the first film; The crystallization temperature of the second film is greater than the crystallization temperature of the first film; the anti-reflection film sub-film layer is cycled N times, wherein the first film is formed when the second film formed in the previous cycle deviates from the One side surface of the substrate layer; after the cycle of the anti-reflection coating sub-layer is completed, a first film is formed on the side surface of the second film farthest from the substrate layer facing away from the substrate layer.

Optionally, the number of cycles N of the anti-reflection coating sub-layer is a natural number greater than or equal to 0.

Optionally, when the thickness of the first film is 5 nm-15 nm, atomic layer deposition is used to form the second film.

Optionally, the total thickness of all the first films in the optical anti-reflection film is 10 nm-80 nm.

Optionally, the first film includes a titanium dioxide film, a zinc oxide film, an indium oxide film or a tin oxide film.

Optionally, the step of forming the first film includes: alternately pulsing the first precursor and the second precursor into the reaction chamber of the atomic layer deposition equipment; the pulse time of the first precursor is 0.5 s-5s, the pulse time of passing into the second precursor is 0.5s-5s; the first precursor includes a first metal compound, the second precursor includes a first oxidant; the first metal compound Including tetrakis(dimethylamino)titanium, tetrakis(ethylmethylamino)titanium, titanium tetrachloride, diethylzinc, dimethylzinc, trimethylindium or tin tetrachloride; the first oxidant Includes water, oxygen or ozone.

Optionally, the step of forming the first film further includes: during the process of alternately passing pulses into the first precursor and the second precursor, always passing a third precursor into the reaction chamber of the atomic layer deposition equipment. A carrier gas; wherein, after the first precursor is introduced into the reaction chamber of the atomic layer deposition equipment and before the second precursor is introduced, the first carrier gas introduced is subjected to a first purge process ; After the second precursor is introduced into the reaction chamber of the atomic layer deposition equipment and before the first precursor is introduced, the first carrier gas introduced is subjected to a second purge process; the first The carrier gas includes nitrogen or helium; the flow rate of the first carrier gas is 800 sccm-1200 sccm; the first purge time is 5s-20s; the second purge time is 5s-20s.

Optionally, the temperature for forming the first film by atomic layer deposition is 150°C-300°C and the pressure is 0.3torr-10torr.

Optionally, the second film includes a silicon dioxide film or an aluminum oxide film.

Optionally, the step of forming the second film includes: alternately pulsing a third precursor and a fourth precursor into the reaction chamber of the atomic layer deposition equipment; the pulse time of the third precursor is 0.5 s-5s, the pulse time of passing into the fourth precursor is 0.5s-5s; the third precursor includes a second metal compound, the fourth precursor includes a second oxidant; the second metal compound Including trimethylaluminum, aluminum trichloride, hexamethylsilanediamine or tris(dimethylamino)silane; the second oxidizing agent includes water, oxygen or ozone.

Optionally, the step of forming the second film further includes: during the process of alternately passing pulses into the third precursor and the fourth precursor, always passing a third precursor into the reaction chamber of the atomic layer deposition equipment. Two carrier gases; wherein, after the third precursor is introduced into the reaction chamber of the atomic layer deposition equipment and before the fourth precursor is introduced, the second carrier gas introduced is subjected to a third purge process ; After the fourth precursor is introduced into the reaction chamber of the atomic layer deposition equipment and before the third precursor is introduced, the second carrier gas introduced is subjected to a fourth purge process; the second The carrier gas includes nitrogen or helium; the flow rate of the second carrier gas is 800 sccm-1200 sccm; the third purge time is 5s-20s; and the fourth purge time is 5s-20s.

Optionally, the temperature and pressure at which the second film is formed by atomic layer deposition are the same as the temperature and pressure at which the first film is formed.

The technical solution of the present invention has the following advantages:

The invention provides a method for preparing an optical anti-reflection film. The anti-reflection film sub-layers are circulated on one side of the substrate layer by atomic layer deposition to form an anti-reflection film, and then the anti-reflection film sub-layers are formed. Under the same temperature conditions as the first film, a second film is formed on the side of the first film facing away from the substrate layer. Since the crystallization temperature of the second film is greater than the crystallization temperature of the first film, when the first film is deposited at the deposition temperature When a film layer is formed and gradually crystallizes, the second film deposited is an amorphous film layer. Materials that are easy to crystallize are more likely to form a crystalline state on the crystal surface, and are more difficult to crystallize on the amorphous layer. Through circulation, the film is enhanced. The film sub-film layer can also improve the crystallization degree of the first film in the current anti-reflection film sub-layer, and can delay the crystallization speed of the first film in the subsequent anti-reflection film sub-layer, thereby inhibiting the crystallization of the first film. degree, effectively reducing the number and size of crystal grains of the first film, thereby increasing the light transmittance of the anti-reflection coating.

By depositing the first film and the second film in the antireflection film sub-layer by atomic layer deposition, the thickness of the first film and the second film can be accurately controlled, and the degree of crystallization of the first film can be further controlled, thereby further improving the The light transmittance of the anti-reflection coating.

Description of the drawings

In order to more clearly explain the specific embodiments of the present invention or the technical solutions in the prior art, the accompanying drawings that need to be used in the description of the specific embodiments or the prior art will be briefly introduced below. Obviously, the drawings in the following description The drawings illustrate some embodiments of the present invention. For those of ordinary skill in the art, other drawings can be obtained based on these drawings without exerting any creative effort.

Figure 1 is a flow chart of a method for preparing an optical antireflection film provided by an embodiment of the present invention;

Figure 2 is a schematic diagram of the surface morphology of the anti-reflection coating under an atomic force microscope (AFM) in Example 1 of the present invention;

Figure 3 is a schematic diagram of the grain size range in Figure 2;

Figure 4 is a schematic diagram of the surface morphology of the antireflection film under an atomic force microscope (AFM) in Comparative Example 1 of the present invention;

Figure 5 is a schematic diagram of the grain size range in Figure 4;

Figure 6 is a comparison chart of the light transmittance of the optical anti-reflection coating in Example 1 of the present invention and Comparative Example 1;

Figure 7 is a schematic diagram of the surface morphology of the anti-reflection coating under an atomic force microscope (AFM) in Example 2 of the present invention;

Figure 8 is a schematic diagram of the grain size range in Figure 7;

Figure 9 is a schematic diagram of the surface morphology of the anti-reflection coating under an atomic force microscope (AFM) in Comparative Example 2 of the present invention;

Figure 10 is a schematic diagram of the grain size range in Figure 9;

Figure 11 is a comparison chart of the light transmittance of the optical anti-reflection coating in Example 2 of the present invention and Comparative Example 2.

Detailed ways

The technical solution of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are some, not all, of the embodiments of the present invention. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts fall within the scope of protection of the present invention.

In the description of the present invention, it should be noted that the terms "center", "upper", "lower", "left", "right", "vertical", "horizontal", "inner", "outer", etc. The indicated orientation or positional relationship is based on the orientation or positional relationship shown in the drawings. It is only for the convenience of describing the present invention and simplifying the description. It does not indicate or imply that the device or element referred to must have a specific orientation or a specific orientation. construction and operation, and therefore should not be construed as limitations of the invention. Furthermore, the terms “first”, “second” and “third” are used for descriptive purposes only and are not to be construed as indicating or implying relative importance.

In the description of the present invention, it should be noted that, unless otherwise clearly stated and limited, the terms "installation", "connection" and "connection" should be understood in a broad sense. For example, it can be a fixed connection or a detachable connection. Connection, or integral connection; it can be a mechanical connection or an electrical connection; it can be a direct connection or an indirect connection through an intermediate medium; it can be an internal connection between two components. For those of ordinary skill in the art, the specific meanings of the above terms in the present invention can be understood on a case-by-case basis.

In addition, the technical features involved in different embodiments of the present invention described below can be combined with each other as long as they do not conflict with each other.

This embodiment provides a method for preparing an optical anti-reflection film. Refer to Figure 1, which includes:

S1: Provides a substrate layer;

S2: Carry out anti-reflection coating sub-layer circulation on one side surface of the substrate layer; the anti-reflection coating sub-layer includes:

S21: Use atomic layer deposition to form the first film;

S22: Use atomic layer deposition to form a second film on the side of the first film away from the substrate layer at the same temperature as the first film; the crystallization temperature of the second film is greater than the the crystallization temperature of the first film;

S3: Cycle the anti-reflection film sub-film layer N times, wherein the first film is formed on the side surface of the second film formed in the previous cycle facing away from the substrate layer;

S4: After the cycle of the anti-reflection coating sub-layer is completed, a first film is formed on the surface of the second film farthest from the substrate layer and facing away from the substrate layer.

In this embodiment, the anti-reflection film is formed by circulating the anti-reflection film sub-layer on one side of the substrate layer using atomic layer deposition, and the first film in the anti-reflection film sub-layer is formed under the same temperature conditions. , a second film is formed on the side of the first film facing away from the substrate layer. Since the crystallization temperature of the second film is greater than the crystallization temperature of the first film, when the first film is deposited at the deposition temperature to form a film layer and gradually forms crystals , the second film formed by deposition is an amorphous film layer, and materials that are easy to crystallize are more likely to form a crystalline state on the crystal surface, but are more difficult to crystallize on the amorphous layer. By recycling the anti-reflection film sub-layer, it can also be improved. The degree of crystallization of the first film in the current anti-reflection film sub-layer can also delay the crystallization speed of the first film in the subsequent anti-reflection film sub-layer, thereby suppressing the degree of crystallization of the first film and effectively reducing the crystallization rate of the first film. The number and size of crystal grains, thereby increasing the light transmittance of the anti-reflection coating.

In one embodiment, the number of cycles N of the anti-reflection coating sub-layer is a natural number greater than or equal to 0, such as 0 times, 1 time, 2 times, 5 times or 15 times. The number of repetitions can be determined based on the required total thickness of the first film in the anti-reflection film and the crystallization characteristics of the first and second film materials in the sub-film layer, and is not specifically limited here.

In one embodiment, the first film includes a titanium dioxide (TiO2) film, a zinc oxide (ZnO) film, an indium oxide (In2O3) film or a tin oxide (SnO2) film; the step of forming the first film includes: The first precursor and the second precursor are alternately pulsed into the reaction chamber of the atomic layer deposition equipment. The first precursor and the second precursor that are alternately introduced in a pulse manner can be on one side surface of the substrate layer, or the side surface of the second film formed in the previous cycle facing away from the substrate layer, That is, one side surface of the previous anti-reflection film sub-layer undergoes chemical adsorption and reaction, thereby forming the first film.

In one embodiment, the first precursor includes a first metal compound and the second precursor includes a first oxidant.

In one embodiment, the first metal compound includes tetrakis(dimethylamino)titanium, tetrakis(ethylmethylamino)titanium, titanium tetrachloride, diethylzinc, dimethylzinc, trimethylzinc Indium or tin tetrachloride; the first oxidant includes water, oxygen or ozone.

In one embodiment, the pulse time for passing the first precursor is 0.5s-5s, such as 0.5s, 1s, 2s, 3s, 4s or 5s, etc.; the pulse time for passing the second precursor is It is 0.5s-5s, such as 0.5s, 1s, 2s, 3s, 4s or 5s, etc.

In one embodiment, the step of forming the first film further includes: during the process of alternately passing pulses into the first precursor and the second precursor, always passing pulses into the reaction chamber of the atomic layer deposition equipment. Inject the first carrier gas; wherein, after the first precursor is introduced into the reaction chamber of the atomic layer deposition equipment and before the second precursor is introduced, the introduced first carrier gas performs a first purge process; to the atomic layer After the second precursor is introduced into the reaction chamber of the deposition equipment and before the first precursor is introduced, the first carrier gas introduced into the reaction chamber undergoes a second purge process. The first carrier gas is continuously introduced into the atomic layer deposition equipment during the step of forming the first film. On the one hand, it may be introduced along with the introduction of the first precursor and the second precursor. To carry the source, the first precursor and the second precursor are carried into the reaction chamber respectively without participating in the reaction; on the other hand, in the gap where the first precursor and the second precursor are alternately introduced, the first carrier gas is introduced The first purge process or the second purge process can be performed to bring the remaining first precursor, second precursor or reaction by-product out of the reaction chamber to ensure film formation quality.

In one embodiment, the first carrier gas includes nitrogen or helium. In other embodiments, the first carrier gas includes other inert gases.

In one embodiment, the flow rate of the first carrier gas is 800 sccm-1200 sccm, for example, it can be 800 sccm, 869 sccm, 925 sccm, 1000 sccm, 1009 sccm, 1102.35 sccm or 1200 sccm, etc.

In one embodiment, the first purge time is 5s-20s, such as 5s, 10s, 15s or 20s; the second purge time is 5s-20s, such as 5s, 10s, 15s or 20s.

In one embodiment, in the process of forming the first film, the temperature at which the first film is formed by atomic layer deposition is 150°C-300°C, such as 150°C, 200°C, 250°C or 300°C; the pressure is 0.3torr-10torr, for example, 0.3torr, 2torr, 4torr, 6torr, 8torr or 10torr, etc.; that is, the deposition temperature of the first film is 150℃-300℃, and the pressure is 0.3torr-10torr.

In one embodiment, the total thickness of all the first films in the optical anti-reflection film is 10 nm-80 nm, such as 10 nm, 20 nm, 30 nm, 40 nm, 50 nm, 60 nm, 70 nm or 80 nm. Specifically, in an anti-reflection coating sub-layer, when the thickness of the first film is 5nm-15nm, for example, it is 5nm, 6nm, 7nm, 8nm, 9nm, 10nm, 11nm, 12nm, 13nm, 14nm or 15nm, etc., The second film is formed using atomic layer deposition. By depositing the first film and the second film in the anti-reflection film sub-layer by atomic layer deposition, the thickness of the first film and the second film can be precisely controlled. By controlling the thickness of the first film, it is deposited when there is a crystallization tendency. Forming a second film and controlling the thickness of the second film to at least 1 nm can improve the effect of the second film on inhibiting the crystallization of the first film, thereby further improving the light transmittance of the anti-reflection film.

The second film includes a silicon dioxide (SiO2) film or an aluminum oxide (Al2O3) film; the step of forming the second film includes: pulse-feeding a third precursor and a fourth precursor alternately into the reaction chamber of the atomic layer deposition equipment. body. The third precursor and the fourth precursor that are alternately introduced in a pulse manner can chemically adsorb and react on the side of the first film facing away from the substrate layer, thereby forming a second film.

In one embodiment, the third precursor includes a second metal compound and the fourth precursor includes a second oxidant.

In one embodiment, the second metal compound includes trimethylaluminum, aluminum trichloride, hexamethylsilane diamine or tris(dimethylamino)silane; the second oxidizing agent includes water, oxygen or ozone.

In one embodiment, the pulse time of the third precursor is 0.5s-5s, for example, 0.5s, 1s, 2s, 3s, 4s or 5s, etc.; the pulse time of the fourth precursor is It is 0.5s-5s, such as 0.5s, 1s, 2s, 3s, 4s or 5s, etc.

In one embodiment, the step of forming the second film further includes: during the process of alternately passing pulses into the third precursor and the fourth precursor, always passing pulses into the reaction chamber of the atomic layer deposition equipment. Injecting the second carrier gas; wherein, after the third precursor is introduced into the reaction chamber of the atomic layer deposition equipment and before the fourth precursor is introduced, the introduced second carrier gas is subjected to a third purge process; to the atomic layer After the fourth precursor is introduced into the reaction chamber of the deposition equipment and before the third precursor is introduced, the second carrier gas introduced into the reaction chamber undergoes a fourth purging process. The second carrier gas is introduced into the atomic layer deposition equipment during the step of forming the second film. On the one hand, it can be introduced along with the introduction of the third precursor and the fourth precursor to play a source-carrying role. , carrying the third precursor and the fourth precursor into the reaction chamber respectively without participating in the reaction; on the other hand, in the gap where the third precursor and the fourth precursor are alternately introduced, the second carrier gas introduced can carry out the third precursor. The third purge treatment and the fourth purge treatment are used to bring the remaining third precursor, fourth precursor or reaction by-products out of the reaction chamber to further ensure the film formation quality.

In one embodiment, the second carrier gas includes nitrogen or helium. In other embodiments, the second carrier gas includes other inert gases.

In one embodiment, the flow rate of the second carrier gas is 800 sccm-1200 sccm, for example, it can be 800 sccm, 869 sccm, 925 sccm, 1000 sccm, 1009 sccm, 1102.35 sccm or 1200 sccm, etc.

In one embodiment, the third purge time is 5s-20s, such as 5s, 10s, 15s or 20s, etc., and the fourth purge time is 5s-20s, such as 5s, 10s, 15s or 20s. wait.

In one embodiment, the temperature and pressure used to form the second film by atomic layer deposition are the same as the temperature and pressure used to form the first film, that is, the deposition temperature of the second film is 150°C-300°C and the pressure is 0.3torr. -10torr, as mentioned above, will not be repeated here.

Example 1

This embodiment is based on the preparation method of the optical anti-reflection film provided in the above embodiment, specifically:

The step of forming the first film includes: pulses alternately passing into the first precursor and the second precursor, using a first carrier gas to perform a first purge process, a second purge process, and After the purge treatment, a first sub-film is formed on one side surface of the substrate layer, that is, the first carrier gas carries the first precursor feed, the first carrier gas performs the first purge treatment, and the first carrier gas The first sub-film is formed by an atomic layer deposition method carrying a second precursor feed and a first carrier gas for a second purge process; the first sub-film is repeated 300 times to form a layer on one side of the substrate layer The first film is formed.

The first precursor includes a first metal compound, and the first metal compound includes one of tetrakis(dimethylamino)titanium, tetrakis(ethylmethylamino)titanium and titanium tetrachloride; The two precursors include a first oxidant, which includes one of water, oxygen, and ozone; and the first film is a titanium dioxide film.

In the process of forming the first film, the deposition temperature of the first film is 250°C and the deposition pressure is 0.5torr; the pulse time of the first metal compound is 1.5s, and the pulse time of the first oxidant is 1.5s; The first carrier gas is nitrogen with a flow rate of 1000 sccm; the first purge time is 8 s; the second purge time is 8 s.

The thickness of the first film is 15 nm.

The step of forming the second film further includes: pulse alternately passing in the third precursor and the fourth precursor, using a second carrier gas to perform a third purge process and a fourth purge process, and in the third After the fourth purge process, a second sub-film is formed on the side surface of the first film facing away from the substrate layer, that is, the third precursor is carried by the second carrier gas, and the second carrier gas is used for the third blow. The second sub-film is formed by an atomic layer deposition method of sweeping treatment, the second carrier gas carries the fourth precursor feed, and the second carrier gas performs the fourth purging treatment; the second sub-film is repeated 80 times to form the second sub-film. A second film is formed on a side surface of the first film facing away from the substrate layer.

The third precursor includes a second metal compound, the second metal compound includes one of hexamethylsilanediamine and tris(dimethylamino)silane; the fourth precursor includes a second oxidant, The second oxidant includes one of water, oxygen and ozone; the second film is a silicon dioxide film.

In the process of forming the second film, the deposition temperature and pressure of the second film are the same as the temperature and pressure of forming the first film, that is: the deposition temperature of the second film is 250°C and the deposition pressure is 0.5torr; The pulse time of the second metal compound is 1.5s, and the pulse time of the second oxidant is 1.5s; the second carrier gas is nitrogen, with a flow rate of 1000 sccm; the third purge time is 8s, and the fourth The purge time is 8s.

The thickness of the second film is 5 nm.

The anti-reflection film sub-film layer is cycled 0 times. After the cycle of the anti-reflection film sub-film layer is completed, a first film is formed on the surface of the second film farthest from the substrate layer facing away from the substrate layer, That is, a 15nm first film is formed on the surface of the 5nm second film, that is, a 15nm first film is formed on the 20nm antireflection film sub-layer, thereby forming a 35nm antireflection film containing Ti, Si, and O. The total thickness of all the first films in the optical anti-reflection film is 30 nm.

Example 2

This embodiment is based on the preparation method of the optical anti-reflection film provided in the above embodiment, specifically:

The step of forming the first film includes: pulses alternately passing into the first precursor and the second precursor, using a first carrier gas to perform a first purge process, a second purge process, and After the purge treatment, a first sub-film is formed on one side surface of the substrate layer, that is, the first carrier gas carries the first precursor feed, the first carrier gas performs the first purge treatment, and the first carrier gas The first sub-film is formed by an atomic layer deposition method carrying a second precursor feed and a first carrier gas for a second purge process; the first sub-film is repeated 55 times to form a layer on one side of the substrate layer The first film is formed.

The first precursor includes a first metal compound, and the first metal compound includes one of diethyl zinc and dimethyl zinc; the second precursor includes a first oxidant, and the second oxidant includes One of water, oxygen and ozone; the first film is a zinc oxide film.

In the process of forming the first film, the deposition temperature of the first film is 150°C and the deposition pressure is 0.7torr; the pulse time of the first metal compound is 1.5s, and the pulse time of the first oxidant is 1.5s; The first carrier gas is nitrogen with a flow rate of 1000 sccm; the first purge time is 8 s; the second purge time is 8 s.

The thickness of the first film is 5 nm.

The step of forming the second film includes: pulse alternately passing the third precursor and the fourth precursor, using a second carrier gas to perform a third purge process, a fourth purge process, and in the fourth After the purge treatment, a second sub-film is formed on the side surface of the first film facing away from the substrate layer, that is, the third precursor is carried by the second carrier gas, and the second carrier gas performs the third purge treatment. The second carrier gas carries the fourth precursor feed, and the second carrier gas performs the fourth purge process to form the second sub-film through atomic layer deposition; repeat the cycle of the first sub-film 12 times to form the second sub-film in the first sub-film. A side surface of the film facing away from the substrate layer forms a second film.

The third precursor includes a second metal compound, the second metal compound includes one of trimethylaluminum and aluminum trichloride; the fourth precursor includes a second oxidant, the second oxidant includes One of water, oxygen and ozone; the second film is an aluminum oxide film.

In the process of forming the second film, the deposition temperature and pressure of the second film are the same as the temperature and pressure of forming the first film, that is: the deposition temperature of the second film is 150°C and the deposition pressure is 0.7torr; The pulse time of the second metal compound is 1.5s, and the pulse time of the second oxidant is 1.5s; the second carrier gas is nitrogen, with a flow rate of 1000 sccm; the third purge time is 8s; the fourth The purge time is 8s.

The thickness of the second film is 1 nm.

Cycle the anti-reflection coating sub-film layer twice, wherein the first film is formed on the side surface of the second film formed in the previous cycle facing away from the substrate layer, that is, the second film at 1 nm A first film of 5nm and a second film of 1nm are formed on the surface in sequence, and a first film of 5nm and a second film of 1nm are formed on the surface of the second film of 1nm, that is, a 6nm anti-reflection film sub-film. Two 6nm anti-reflection coating sub-layers are formed on the layer.

After the anti-reflection coating sub-layer cycle ends, a first film is formed on the surface of the second film farthest from the substrate layer facing away from the substrate layer, that is, a 5 nm first film is formed sequentially again, That is, a 5nm first film is formed on the third 6nm anti-reflection coating sub-layer. Thus, a 23 nm anti-reflection film containing Zn, Al, and O is formed, and the total thickness of all the first films in the optical anti-reflection film is 20 nm.

Comparative example 1

Comparative Example 1 provides a method for preparing an optical anti-reflection coating, including:

providing a backing layer;

A first film is formed on one side of the substrate layer using atomic layer deposition.

The step of forming the first film includes: pulses alternately passing into the first precursor and the second precursor, using a first carrier gas to perform a first purge process, a second purge process, and After the purge treatment, the first sub-film is formed on one side surface of the substrate layer, that is, the first precursor is carried by the first carrier gas, the first carrier gas performs the first purge treatment, and the first carrier gas is used to carry out the first precursor feed. The first sub-film is formed by an atomic layer deposition method in which the gas carries the second precursor feed and the first carrier gas performs the second purge process; the first sub-film is repeated 600 times to form a layer on one side of the substrate layer A first film is formed on the surface.

In the process of forming the first film, the deposition temperature of the first film is 250°C and the deposition pressure is 0.5torr; the pulse time of the first metal compound is 1.5s, and the pulse time of the first oxidant is 1.5s; The first carrier gas is nitrogen with a flow rate of 1000 sccm; the time of the first purge process and the time of the second purge process are both 8 seconds.

The first metal compound includes one of tetrakis(dimethylamino)titanium, tetrakis(ethylmethylamino)titanium and titanium tetrachloride; the first oxidizing agent includes one of water, oxygen and ozone. ; The first film is a titanium dioxide film.

Thus, a 30 nm anti-reflection film containing Ti and O is formed, and the total thickness of all the first films in the optical anti-reflection film is 30 nm.

Comparative example 2

Comparative Example 2 provides a method for preparing an optical anti-reflection coating, including:

providing a backing layer;

A first film is formed on one side of the substrate layer using atomic layer deposition.

The step of forming the first film includes: pulse-feeding the first metal compound and the first oxidant alternately, using a first carrier gas to perform a first purge process, a second purge process, and performing a second purge process on the second film. After the sweeping process, the first sub-film is formed on one side surface of the substrate layer, that is, the first precursor is carried by the first carrier gas, the first carrier gas performs the first purging process, and the first carrier gas The first sub-film is formed by an atomic layer deposition method carrying a second precursor feed and a first carrier gas for a second purge process; the first sub-film is repeated 220 times to form a layer on one side of the substrate layer The first film is formed.

In the process of forming the first film, the deposition temperature of the first film is 150°C and the deposition pressure is 0.7torr; the pulse time of the first metal compound is 1.5s, and the pulse time of the first oxidant is 1.5s; the pulse time of the first metal compound is 1.5s; The first carrier gas is nitrogen with a flow rate of 1000 sccm; the time of the first purge process and the time of the second purge process are both 8 seconds.

The first metal compound includes one of diethyl zinc and dimethyl zinc; the first oxidant includes one of water, oxygen and ozone; and the first film is a zinc oxide film.

Thus, a 20 nm anti-reflection film containing Zn and O is formed, and the total thickness of all the first films in the optical anti-reflection film is 20 nm.

Comparing Example 1 with Comparative Example 1, and comparing Example 2 with Comparative Example 2, it was found that under the same substrate layer and deposition conditions, such as the same deposition temperature, pressure, pulse time, and carrier gas purge time, Example 1 and Example 2 adopt the preparation method of the optical anti-reflection film provided by the present invention: the anti-reflection film sub-layer is circulated on one side of the substrate layer; the anti-reflection film sub-layer includes: using atoms The first film is formed by layer deposition; the second film is formed on the side of the first film away from the substrate layer by atomic layer deposition and at the same temperature used to form the first film; and Example 1 and Comparative Example 2 formed the first film only on one side surface of the substrate layer.

Combining Figures 2 to 5 and referring to Figure 6, the maximum range of the surface morphology of the Ti-containing anti-reflection coating dropped from 38.4nm to 3.9nm, which effectively improved the crystallization degree of the anti-reflection coating and effectively improved the anti-reflection coating at 400 Transmittance in the wavelength range of ~600nm.

Combining Figures 7 to 10 and referring to Figure 11, the maximum range of the surface morphology of the Zn-containing antireflection coating dropped from 24.5nm to 2.9nm, which effectively improved the crystallization degree of the antireflection coating and effectively improved the performance of the antireflection coating at 400 Transmittance in the wavelength range of ~800nm.

To sum up, the optical anti-reflection film obtained by using the preparation method of the optical anti-reflection film of the present invention is circulated through the anti-reflection film sub-layer on one side of the substrate layer. Specifically, the anti-reflection film sub-layer is The method includes: forming a first film on one side surface of the substrate layer; forming a second film on the side of the first film facing away from the substrate layer at the same temperature at which the first film is formed, and cycling N times The anti-reflection film sub-layer can inhibit the degree of crystallization of the first film, thereby effectively reducing the number and size of crystal grains of the first film, thereby increasing the light transmittance of the anti-reflection film.

Obviously, the above-mentioned embodiments are only examples for clear explanation and are not intended to limit the implementation. For those of ordinary skill in the art, other different forms of changes or modifications can be made based on the above description. An exhaustive list of all implementations is neither necessary nor possible. The obvious changes or modifications derived therefrom are still within the protection scope of the present invention.

Claims (12)

1. A method for preparing an optical antireflection film, comprising:

providing a substrate layer;

recycling an antireflection film sub-film layer on one side surface of the substrate layer; the antireflection film sub-film layer comprises:

forming a first film by using an atomic layer deposition mode; forming a second film on the side of the first film away from the substrate layer by using an atomic layer deposition mode and at the same temperature as the first film; the crystallization temperature of the second film is greater than the crystallization temperature of the first film;

cycling the antireflection film sub-film layer for N times, wherein the first film is formed on one side surface of the second film formed in the previous cycle, which is away from the substrate layer;

and after the circulation of the antireflection film sub-film layer is finished, forming a first film on the surface of one side of the second film farthest from the substrate layer, which is away from the substrate layer.

2. The method for producing an optical antireflection film according to claim 1, wherein the number of cycles of the antireflection film sub-film layer N is a natural number of 0 or more.

3. The method of manufacturing an optical antireflection film according to claim 1, wherein the second film is formed using atomic layer deposition when the thickness of the first film is 5nm to 15nm.

4. The method of producing an optical antireflection film according to claim 1, wherein the total thickness of all the first films in the optical antireflection film is 10nm to 80nm.

5. The method of manufacturing an optical antireflection film according to claim 1, wherein the first film comprises a titanium oxide film, a zinc oxide film, an indium oxide film, or a tin oxide film.

6. The method of producing an optical antireflection film according to claim 1, wherein the step of forming the first film comprises: alternately introducing a first precursor and a second precursor into a reaction cavity of the atomic layer deposition equipment in a pulse mode;

the pulse time of the first precursor is 0.5s-5s, and the pulse time of the second precursor is 0.5s-5s;

the first precursor comprises a first metal compound and the second precursor comprises a first oxidant; the first metal compound includes tetra (dimethylamino) titanium, tetra (ethylmethylamino) titanium, titanium tetrachloride, diethyl zinc, dimethyl zinc, trimethyl indium, or tin tetrachloride; the first oxidant comprises water, oxygen or ozone.

7. The method of manufacturing an optical antireflection film according to claim 6, wherein the step of forming the first film further comprises: in the process of alternately introducing the first precursor and the second precursor by pulses, first carrier gas is always introduced into a reaction cavity of atomic layer deposition equipment;

after the first precursor is introduced into the reaction cavity of the atomic layer deposition equipment and before the second precursor is introduced, the first carrier gas is introduced to perform first purging treatment; after the second precursor is introduced into the reaction cavity of the atomic layer deposition equipment and before the first precursor is introduced, the introduced first carrier gas carries out second purging treatment;

the first carrier gas comprises nitrogen or helium; the flow rate of the first carrier gas is 800sccm-1200sccm;

the first purging time is 5s-20s; the second purge time is 5s-20s.

8. The method of claim 6 or 7, wherein the atomic layer deposition is performed at a temperature of 150 ℃ to 300 ℃ and a pressure of 0.3torr to 10torr.

9. The method of manufacturing an optical antireflection film according to claim 8, wherein the second film comprises a silica film or an alumina film.

10. The method of producing an optical antireflection film according to claim 8, wherein the step of forming the second film comprises: alternately introducing a third precursor and a fourth precursor into a reaction cavity of the atomic layer deposition equipment in a pulse mode;

the pulse time of the third precursor is 0.5s-5s, and the pulse time of the fourth precursor is 0.5s-5s;

the third precursor comprises a second metal compound and the fourth precursor comprises a second oxidant; the second metal compound includes trimethylaluminum, aluminum trichloride, hexamethylenediamine, or tris (dimethylamino) silane; the second oxidant comprises water, oxygen or ozone.

11. The method of producing an optical antireflection film according to claim 10, wherein the step of forming the second film further comprises: in the process of alternately introducing the third precursor and the fourth precursor by pulses, introducing a second carrier gas into a reaction cavity of the atomic layer deposition equipment all the time;

after the third precursor is introduced into the reaction cavity of the atomic layer deposition equipment and before the fourth precursor is introduced, the introduced second carrier gas carries out third purging treatment; after the fourth precursor is introduced into the reaction cavity of the atomic layer deposition equipment and before the third precursor is introduced, the introduced second carrier gas carries out fourth purging treatment;

the second carrier gas comprises nitrogen or helium; the flow rate of the second carrier gas is 800sccm-1200sccm;

the third purging time is 5s-20s; the fourth purge time is 5s-20s.

12. The method of producing an optical antireflection film according to claim 10 or 11, wherein the temperature and pressure at which the second film is formed by atomic layer deposition are the same as the temperature and pressure at which the first film is formed.