CN119024467A

CN119024467A - Anti-reflection device, preparation method of anti-reflection device and application thereof

Info

Publication number: CN119024467A
Application number: CN202411234192.2A
Authority: CN
Inventors: 李翔; 袁红霞; 姚俊; 李鹏; 陈昌
Original assignee: Jiangsu Leadmicro Nano Technology Co Ltd
Current assignee: Jiangsu Leadmicro Nano Technology Co Ltd
Priority date: 2024-09-03
Filing date: 2024-09-03
Publication date: 2024-11-26

Abstract

The disclosure provides an anti-reflection device, a preparation method and application of the anti-reflection device. The anti-reflection device comprises a substrate and an anti-reflection film layer structure which is arranged on the substrate in a laminated mode, wherein the anti-reflection film layer structure comprises an anti-reflection base layer and an anti-reflection enhancement layer which is arranged on the anti-reflection base layer in a laminated mode, and the anti-reflection enhancement layer comprises a metal-based organic hybrid film with a porous structure. The metal-based organic hybrid film can enhance the anti-reflection effect of the anti-reflection base layer, which is advantageous in that the number of film layers required in the anti-reflection base layer is reduced while maintaining the device to have a low reflectivity, so that the structure of the anti-reflection base layer is simplified.

Description

Antireflection device, preparation method and application of antireflection device

Technical Field

The invention relates to the technical field of antireflection films, in particular to an antireflection device, a preparation method and application of the antireflection device.

Background

The antireflection film is also called an antireflection film, and is mainly used for eliminating reflected light on the surfaces of devices such as lenses, prisms, plane mirrors and the like, increasing the light transmission quantity of the devices and reducing or eliminating stray light of the system.

The antireflection film mainly utilizes the interference cancellation principle of light rays, and is matched in modes of refractive index matching, thickness design, selection of special materials and the like of different materials so as to reduce reflected light and increase transmitted light. A major feature of such optical antireflection films is that a greater number of films are often required to form a laminate structure if lower reflectivity is desired. For example, in some conventional techniques, if it is desired to reduce the reflectance of the lens to 0.5% or less, a laminated structure composed of 9 or more thin films is required. Therefore, the structure of the antireflection film in the conventional art is generally complicated.

Disclosure of Invention

Based on this, it is necessary to provide an antireflection device in which the antireflection film layer structure can be simplified, in view of the problems in the background art described above.

According to some embodiments of the present disclosure, there is provided an anti-reflection device including a substrate and an anti-reflection film layer structure stacked on the substrate, the anti-reflection film layer structure including an anti-reflection base layer and an anti-reflection enhancement layer stacked on the anti-reflection base layer, the anti-reflection enhancement layer including a metal-based organic hybrid film having a porous structure.

In some embodiments of the present disclosure, the anti-reflection enhancing layer is the metal-based organic hybrid film; or alternatively

The anti-reflection enhancement layer comprises at least one layer of the metal-based organic hybridization film and at least one layer of metal oxide film, the material of the metal oxide film comprises metal oxide, and the metal-based organic hybridization film and the metal oxide film are alternately laminated.

In some embodiments of the present disclosure, the material of the metal oxide film includes one or more of aluminum oxide, zinc oxide, and titanium oxide.

In some embodiments of the disclosure, the total equivalent refractive index of the anti-reflection enhancing layer is 1.2 to 1.5.

In some embodiments of the present disclosure, the anti-reflection enhancing layer satisfies at least one of the following features:

(1) The thickness of the anti-reflection enhancement layer is 10 nm-200 nm;

(2) The aperture of the pore in the anti-reflection enhancement layer is 1 nm-30 nm;

(3) The porosity of the anti-reflection enhancement layer is 10% -70%.

In some embodiments of the present disclosure, the material of the metal-based organic hybrid film includes one or more of an aluminum-based hydroquinone hybrid material, a zinc-based hydroquinone hybrid material, and a titanium-based hydroquinone hybrid material.

In some embodiments of the present disclosure, the metal-based organic hybrid film is prepared by deposition of a molecular layer.

In some embodiments of the present disclosure, the metal-based organic hybrid film is prepared from a starting material comprising a first metal precursor and an organic precursor; wherein,

The first metal precursor is selected from one or more of trimethylaluminum, zinc acetate and titanium tetrachloride, and the organic precursor is selected from hydroquinone.

In some embodiments of the present disclosure, the antireflective base layer comprises a high refractive index film and a low refractive index film, the high refractive index film having a higher refractive index than the low refractive index film;

the high refractive index film and the low refractive index film each have at least one layer, and the high refractive index film and the low refractive index film are alternately laminated.

In some embodiments of the present disclosure, the total number of film layers of the high refractive index film and the low refractive index film is 2 to 4.

In some embodiments of the present disclosure, the average reflectivity of the antireflection film layer structure for light rays in the 400 nm-800 nm band is below 0.2%.

In a second aspect, the present disclosure also provides a method for manufacturing the above-mentioned anti-reflection device, which provides a substrate;

Preparing an anti-reflection base layer on the substrate;

Placing the substrate in a deposition chamber, and preparing an anti-reflection enhancing layer on the substrate, wherein the step of preparing the anti-reflection enhancing layer comprises: depositing to form the metal-based organic hybrid film with a porous structure.

In some embodiments of the present disclosure, the manner of depositing the metal-based organic hybrid material is a molecular layer deposition method.

In some embodiments of the present disclosure, the step of preparing the anti-reflection enhancing layer further comprises depositing a metal oxide film, and the step of depositing a metal-based organic hybrid film and the step of depositing a metal oxide film are performed alternately.

In some embodiments of the present disclosure, the step of depositing to form a metal-based organic hybrid film comprises: introducing a first metal precursor into a deposition chamber and enabling the first metal precursor to be attached to the substrate to form a first monomolecular layer, and introducing an organic precursor into the deposition chamber and enabling the organic precursor to be attached to the substrate to form a second monomolecular layer;

The step of depositing a metal oxide material includes: introducing a second metal precursor into the deposition chamber and enabling the second metal precursor to be attached to the substrate to form a third monomolecular layer, and introducing an oxidant into the deposition chamber and enabling the oxidant to be attached to the substrate to form a fourth monomolecular layer;

taking the whole of the step of forming the first monolayer and the step of forming the second monolayer as a first deposition cycle, and taking the whole of the step of forming the third monolayer and the step of forming the fourth monolayer as a second deposition cycle;

At least one first deposition cycle is continuously performed to form a metal-based organic hybrid film, at least one second deposition cycle is continuously performed to form a metal oxide film, and at least one metal-based organic hybrid film and at least one metal oxide film are alternately formed.

In some embodiments of the present disclosure, the first metal precursor is selected from one or more of trimethylaluminum, ethylene-di-zinc, and titanium tetrachloride, and the organic precursor is selected from hydroquinone; and/or the number of the groups of groups,

The second metal precursor is selected from one or more of trimethylaluminum, zinc acetate and titanium tetrachloride, and the oxidant is selected from one or more of water and oxygen.

In some embodiments of the present disclosure, the ratio of the number of times the first deposition cycle is performed to the number of times the second deposition cycle is performed is 1 (1-5).

In some embodiments of the present disclosure, the number of first deposition cycles is 40-500.

In some embodiments of the present disclosure, in the step of depositing the metal-based organic hybrid film, the temperature of the deposition chamber is controlled to be 150 ℃ to 300 ℃.

In some embodiments of the present disclosure, the step of preparing an anti-reflective base layer on the substrate comprises:

alternately depositing a high refractive index film and a low refractive index film on the substrate, wherein the refractive index of the high refractive index film is higher than that of the low refractive index film, and at least one layer of the high refractive index film and the low refractive index film is arranged on the substrate.

In a third aspect, the present disclosure also provides a use of a metal-based organic hybrid film in an antireflection film layer structure comprising an antireflection enhancement layer comprising the metal-based organic hybrid film, the metal-based organic hybrid film having a porous structure.

In some embodiments of the present disclosure, the metal-based organic hybrid film comprises the anti-reflection enhancing layer; or alternatively

(1) The thickness of the anti-reflection enhancement layer is 10 nm-200 nm;

(3) The porosity of the anti-reflection enhancement layer is 10% -70%.

An antireflection film layer structure is provided in an antireflection device of the present disclosure, the antireflection film layer structure including an antireflection base layer and an antireflection enhancement layer laminated on the antireflection base layer. The anti-reflection enhancing layer includes a metal-based organic hybrid film having a porous structure. In the research process, the applicant finds that the porous structure in the metal-based organic hybrid film can enable the refractive index of the porous structure to be between that of air and that of other material layers in the antireflection film layer structure, and the porous structure in the metal-based organic hybrid film enables the refractive index of the porous structure to have the characteristic of gradual change along with the thickness, which is equivalent to the arrangement of multiple layers of films with different refractive indexes in a laminated manner, so that the metal-based organic hybrid film can play a role in reducing the reflectivity performance, and the effect of arranging multiple layers of films in the traditional technology can be achieved. Thanks to the above characteristics, the metal-based organic hybrid film can enhance the antireflection effect of the antireflection base layer, which is advantageous in that the number of film layers required in the antireflection base layer is reduced while maintaining the device having a low reflectance, so that the structure of the antireflection base layer is simplified.

Further, in at least some embodiments of the present disclosure, metal-based organic hybrid films can be prepared by way of molecular layer deposition, and can be directly formed into a desired porous structure during deposition. Compared with the traditional design of the multilayer film, the metal-based organic hybrid film is adopted to participate in forming the antireflection film layer structure, the whole process is simpler, the process difficulty is lower, and the realization is easy.

In addition, the metal-based organic hybrid film can be formed by molecular layer deposition. The control on the porosity and the pore distribution can be realized by controlling the temperature in the deposition process, the thickness and other conditions of the metal-based organic hybrid film, or by superposing other metal oxide films on the surface of the pore wall of the hole in the metal-based organic hybrid film, so that the refractive index of the metal-based organic hybrid film can be adjusted. The metal-based organic hybrid film is beneficial to widening the application range of the metal-based organic hybrid film, so that the metal-based organic hybrid film can be matched with various different anti-reflection base layers to form an anti-reflection film layer structure with extremely low reflectivity.

The foregoing description is only an overview of the present invention, and is intended to provide a better understanding of the present invention, as it is embodied in the following description, with reference to the preferred embodiments of the present invention and the accompanying drawings.

Drawings

In order to more clearly illustrate the technical solutions of the embodiments of the present disclosure, the drawings required for the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present disclosure, and that other embodiments of the drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.

FIG. 1 is a schematic diagram of an exemplary structure of an anti-reflection device;

FIG. 2 is a schematic diagram of an anti-reflective device according to another embodiment;

FIG. 3 is a graph showing reflectance of the coated glass according to wavelength in comparative example 3;

fig. 4 shows a graph of reflectance as a function of wavelength for the coated glasses of examples 2.1 and 2.2.

Wherein, each reference sign and meaning are as follows:

100. A substrate; 110. an anti-reflection enhancement layer; 120. an anti-reflection base layer; 121. a high refractive index film; 122. a low refractive index film; 200. a substrate; 210. an anti-reflection enhancement layer; 220. an anti-reflection base layer; 221. a high refractive index film; 222. a low refractive index film.

Detailed Description

To facilitate an understanding of this document, a more complete description of this document will follow. Preferred embodiments herein are presented. This may be embodied in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description presented herein is for the purpose of describing particular embodiments only and is not intended to be limiting.

It will be understood that when an element or layer is referred to as being "on," "adjacent," "connected to," or "coupled to" another element or layer, it can be directly on, adjacent, connected, or coupled to the other element or layer, or intervening elements or layers may also be present. In contrast, when an element is referred to as being "directly on," "directly adjacent to," "directly connected to," or "directly coupled to" another element or layer, there are no intervening elements or layers present. It will be understood that, although the terms first, second, third, etc. may be used herein to describe various elements, components, regions, layers and/or sections, these elements, components, regions, layers and/or sections should not be limited by these terms. These terms are only used to distinguish one element, component, region, layer or section from another element, component, region, layer or section.

Spatially relative terms, such as "under", "below", "beneath", "under", "above", "over" and the like, may be used herein for ease of description to describe one element or feature's relationship to another element or feature. It will be understood that the spatially relative terms are intended to encompass different orientations of the device in use and operation. For example, if the device in the figures is turned over, elements or features described as "under" or "beneath" other elements would then be oriented "on" the other elements or features. Thus, the exemplary terms "below" and "under" may include both an upper and a lower orientation. The device may be otherwise oriented (e.g., rotated 90 degrees or other orientations) and the spatial descriptors used herein interpreted accordingly.

The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the disclosure. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise. It will be further understood that the terms "comprises" and/or "comprising," when used in this specification, specify the presence of stated features, integers, steps, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, and/or groups thereof. As used herein, the term "and/or" includes any and all combinations of the associated listed items.

Conventional antireflection films generally need to include a plurality of films, and the reflectivity of light is reduced by refractive index variation of the plurality of films and corresponding thickness.

The present disclosure provides an anti-reflection device including a substrate and an anti-reflection film layer structure stacked on the substrate, the anti-reflection film layer structure including an anti-reflection enhancement layer including a metal-based organic hybrid film having a porous structure.

As an example of this embodiment, the anti-reflection enhancing layer may be a metal-based organic hybrid film.

As another example of this embodiment, the anti-reflection enhancing layer includes at least one metal-based organic hybrid film and at least one metal oxide film, and the material of the metal oxide film includes a metal oxide, and the metal-based organic hybrid film and the metal oxide film are alternately stacked. It is understood that each layer of metal-based organic hybrid film may have a porous structure, and each layer of metal oxide film may be attached to the pore wall surface in the immediately adjacent metal-based organic hybrid film.

It is understood that the anti-reflective base layer may refer to a film layer having an anti-reflective effect known in the present disclosure. As an example of this embodiment, the antireflection base layer includes a high refractive index film and a low refractive index film, the high refractive index film having a higher refractive index than the low refractive index film. The high refractive index film and the low refractive index film are each provided with at least one layer, and the high refractive index film and the low refractive index film are alternately laminated. The reflectivity of the substrate on which the high refractive index film and the low refractive index film are formed can be reduced by the laminated structure.

As an example of this embodiment, at least one layer of each of the high refractive index film and the low refractive index film is provided, and the high refractive index film and the low refractive index film are alternately laminated. It will be appreciated that as the number of layers of the high refractive index film and the low refractive index film increases, the anti-reflection effect of the anti-reflection base layer formed by the high refractive index film and the low refractive index film can be enhanced, but this also increases the structural complexity of the anti-reflection base layer and makes the manufacturing process more complex accordingly.

As an example of this embodiment, the number of high refractive index films and low refractive index films is the same, and among the antireflection base layers, the high refractive index film is disposed closest to the substrate, and the low refractive index film is disposed closest to the antireflection enhancement layer.

In some examples, the total number of layers of the high refractive index film and the low refractive index film is 2 to 4 layers, which is advantageous in simplifying the structure of the antireflection base layer as much as possible. Also, as will be described later, even with the antireflection base layer of simple structure in this example, by providing the antireflection enhancement layer correspondingly, the antireflection film layer structure as a whole can be made to have significantly lower reflectance.

Fig. 1 is a schematic structural view of an anti-reflection device of the present disclosure. Referring to fig. 1, the anti-reflection device includes a substrate 100 and an anti-reflection film layer structure stacked on the substrate 100, the anti-reflection film layer structure including an anti-reflection base layer 120 and an anti-reflection enhancing layer 110 stacked on the anti-reflection base layer 120, the anti-reflection enhancing layer 110 including a metal-based organic hybrid film having a porous structure.

In the embodiment shown in fig. 1, the antireflective base layer 120 includes a high refractive index film 121 and a low refractive index film 122. Wherein the refractive index of the high refractive index film 121 is higher than that of the low refractive index film 122.

As an example of this embodiment, the substrate 100 may be a workpiece carrying the anti-reflective film layer structure. The workpiece may be, but is not limited to, an optical lens. The material of the optical lens can be organic glass or inorganic glass.

In some examples, the organic glass is plexiglass and the inorganic glass is K9 glass.

Referring to fig. 1, in this embodiment, in the antireflection base layer 120, the film at the bottom layer is a high refractive index film 121, and the film at the top layer is a low refractive index film 122.

As an example of this embodiment, the refractive index of the high refractive index film 121 is 1.5 or more. Further, the refractive index of the high refractive index film 121 is 1.5 to 2.3.

As an example of this embodiment, the material of the high refractive index film 121 includes one or more of titanium oxide (TiO ₂), aluminum oxide (Al ₂O₃), tantalum oxide (Ta ₂O₃), and zirconium oxide (ZrO ₂). Wherein the refractive index of the titanium oxide is about 2.31, the refractive index of the aluminum oxide is about 1.62, the refractive index of the tantalum oxide is about 2.11, and the refractive index of the zirconium oxide is about 2.15. It will be appreciated that the refractive index of the high refractive index film 121 is related to its material, and that the material of the high refractive index film 121 may be selected corresponding to a desired refractive index.

As an example of this embodiment, the thickness of the high refractive index film 121 is 3nm to 30nm. In some examples, the thickness of the high refractive index film 121 may be 3nm, 5nm, 6nm, 7nm, 8nm, 10nm, 12nm, 15nm, 17nm, 20nm, 25nm, 30nm, or the thickness of the high refractive index film 121 may be between any two of the above.

As an example of this embodiment, the refractive index of the low refractive index film 122 is equal to or less than 1.5. Further, the refractive index of the low refractive index film 122 is 1.35 to 1.5.

As an example of this embodiment, the material of the low refractive index film 122 includes one or more of silicon oxide (SiO ₂) and magnesium fluoride (MgF ₂). Wherein the refractive index of the silicon oxide is about 1.45 and the refractive index of the magnesium fluoride is about 1.38. It will be appreciated that the refractive index of the low refractive index film 122 is related to its material, and that the material of the low refractive index film 122 may be selected to correspond to a desired refractive index.

As an example of this embodiment, the thickness of the low refractive index film 122 is 40nm to 120nm.

In some examples, the thickness of the low refractive index film 122 may be 40nm, 50nm, 60nm, 70nm, 80nm, 90nm, 100nm, 110nm, 120nm, or the thickness of the low refractive index film 122 may be between any two of the above thicknesses.

Referring to fig. 1, as an example of this embodiment, the anti-reflection enhancing layer 110 is a metal-based organic hybrid film.

It is understood that the refractive index of the metal-based organic hybrid film may gradually vary along the thickness direction, but the metal-based organic hybrid film has an equivalent refractive index as a whole. As an example of this embodiment, the equivalent refractive index of the anti-reflection enhancing layer 110 is 1.2 to 1.5, that is, the equivalent refractive index of the metal-based organic hybrid film of this embodiment is 1.2 to 1.5.

Further, in this embodiment, the equivalent refractive index of the metal-based organic hybrid film is 1.23 to 1.3. The metal-based organic hybrid film with the equivalent refractive index in the range can play a role in obviously better enhancing the anti-reflection effect, and is beneficial to obtaining an anti-reflection film layer structure with obviously lower reflectivity.

In some examples, the equivalent refractive index of the metal-based organic hybrid film may be 1.23, 1.24, 1.25, 1.26, 1.27, 1.28, 1.29, 1.3, or the equivalent refractive index of the metal-based organic hybrid film may be between any two of the refractive indices described above.

In general, the equivalent refractive index of the metal-based organic hybrid membrane is related to the thickness of the membrane, the pore diameter of the pores, the porosity and other factors.

As an example of this embodiment, the thickness of the metal-based organic hybrid film is 10nm to 200nm.

In some examples, the thickness of the metal-based organic hybrid film may be 10nm, 20nm, 30nm, 40nm, 50nm, 60nm, 70nm, 80nm, 100nm, 120nm, 150nm, 200nm, or the thickness of the metal-based organic hybrid film may be between any two of the above thicknesses.

As an example of this embodiment, the pore diameter of the pores in the metal-based organic hybrid film is 1nm to 30nm.

In some examples, the pore size of the pores in the metal-based organic hybrid membrane is about 1nm, 2nm, 3nm, 5nm, 7nm, 10nm, 12nm, 14nm, 15nm, 17nm, 20nm, 25nm, 30nm, or the pore size of the pores in the metal-based organic hybrid membrane may be between any two of the pore sizes described above.

As an example of this embodiment, the porosity of the metal-based organic hybrid film is 10% -70%.

In some examples, the porosity of the metal-based organic hybrid film is 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, or the porosity of the metal-based organic hybrid film may also be between any two of the porosities described above.

As an example of this embodiment, the material of the metal-based organic hybrid film includes one or more of an aluminum-based hydroquinone hybrid material, a zinc-based hydroquinone hybrid material, and a titanium-based hydroquinone hybrid material. Wherein the aluminum-based hydroquinone hybrid material can be obtained by reacting an aluminum compound with hydroquinone, and the aluminum compound can include, but is not limited to, trimethylaluminum. The zinc-based hydroquinone hybrid material may be obtained by reacting a zinc compound with hydroquinone, which may include, but is not limited to, diethyl zinc. The titanium-based hydroquinone hybrid material may be obtained by reacting a titanium compound, which may include, but is not limited to, titanium tetrachloride, with hydroquinone.

As an example of this embodiment, a metal-based organic hybrid film is prepared by deposition of a molecular layer. In the molecular layer deposition process, the formed metal-based organic hybrid film can directly form a porous structure. By controlling the temperature in the deposition process, the deposition cycle times and other conditions, the porous structure in the metal-based organic hybrid film can be correspondingly controlled.

As an example of this embodiment, the preparation raw material of the metal-based organic hybrid film includes a first metal precursor and an organic precursor. Wherein the first metal precursor is selected from one or more of trimethylaluminum, zinc acetate and titanium tetrachloride, and the organic precursor is selected from hydroquinone.

It will be appreciated that the materials of the metal-based organic hybrid film are related to the raw materials from which they are prepared. For example, if the material of the metal-based organic hybrid film comprises an aluminum-based hydroquinone hybrid material, the first metal precursor may be trimethylaluminum and the organic precursor may be hydroquinone. If the material of the metal-based organic hybrid film comprises a zinc-based hydroquinone hybrid material, the first metal precursor may be ethylene di-zinc and the organic precursor may be hydroquinone. If the material of the metal-based organic hybrid film comprises a titanium-based hydroquinone hybrid material, the first metal precursor may be titanium tetrachloride and the organic precursor may be hydroquinone.

As an example of this embodiment, the average reflectance of the antireflection film layer structure for light rays in the 400nm to 800nm band is 0.2% or less.

Fig. 2 is a schematic structural view of another anti-reflection device of the present disclosure. Referring to fig. 2, the anti-reflection device includes a substrate 200 and an anti-reflection film layer structure stacked on the substrate 200, the anti-reflection film layer structure including an anti-reflection base layer 220 and an anti-reflection enhancing layer 210 stacked on the anti-reflection base layer 220, the anti-reflection enhancing layer 210 including a metal-based organic hybrid film having a porous structure. In the embodiment shown in fig. 2, the antireflective base layer 220 includes two high refractive index films 221 and two low refractive index films 222. Wherein the refractive index of the high refractive index film 221 is higher than that of the low refractive index film 222.

In this embodiment, the refractive index and thickness of the two high refractive index films 221 may be different, as may the refractive index and thickness of the two low refractive index films 222, depending primarily on the desired structural design of the antireflective base layer 220.

As an example of this embodiment, the substrate 200 may be a workpiece carrying the anti-reflective film layer structure. The workpiece may be, but is not limited to, an optical lens. The material of the optical lens can be organic glass or inorganic glass.

Referring to fig. 2, in this embodiment, in the anti-reflection base layer 220, the film located at the bottom layer is a high refractive index film 221, and the film located at the top layer is a low refractive index film 222.

As an example of this embodiment, the refractive index of the high refractive index film 221 is 1.5 or more. Further, the refractive index of the high refractive index film 221 is 1.5 to 2.3.

As an example of this embodiment, the material of the high refractive index film 221 includes one or more of titanium oxide, aluminum oxide, tantalum oxide, and zirconium oxide.

As an example of this embodiment, the thickness of the high refractive index film 221 is 3nm to 30nm.

As an example of this embodiment, the refractive index of the low refractive index film 222 is equal to or less than 1.5. Further, the refractive index of the low refractive index film 222 is 1.35 to 1.5.

As an example of this embodiment, the material of the low refractive index film 222 includes one or more of silicon oxide and magnesium fluoride.

As an example of this embodiment, the thickness of the low refractive index film 222 is 40nm to 120nm.

Referring to fig. 2, as an example of this embodiment, the anti-reflection enhancing layer 210 includes at least one metal-based organic hybrid film and at least one metal oxide film, and the material of the metal oxide film includes a metal oxide, and the metal-based organic hybrid film and the metal oxide film are alternately stacked. The introduction of the metal oxide film can realize the regulation and control of the pore structure in the anti-reflection enhancing layer 210, thereby enriching the performance of the anti-reflection enhancing layer 210.

Further, each layer of metal-based organic hybrid film may have a porous structure, and each layer of metal oxide film may be attached to the pore wall surface in the immediately adjacent metal-based organic hybrid film.

As an example of this embodiment, the equivalent refractive index of the anti-reflection enhancing layer 210 is 1.2 to 1.5, that is, the equivalent refractive index of the stacked structure composed of the metal-based organic hybrid film and the metal oxide film of this embodiment is 1.2 to 1.5.

Further, in this embodiment, the equivalent refractive index of the anti-reflection enhancing layer 210 is 1.23 to 1.3. The anti-reflection enhancement layer 210 with the equivalent refractive index in the range can play a role in enhancing anti-reflection remarkably better, and is beneficial to obtaining an anti-reflection film layer structure with remarkably lower reflectivity.

In some examples, the equivalent refractive index of the anti-reflection enhancing layer 210 may be 1.23, 1.24, 1.25, 1.26, 1.27, 1.28, 1.29, 1.3, or the equivalent refractive index of the anti-reflection enhancing layer 210 may be between any two of the refractive indices described above.

Overall, the equivalent refractive index of the anti-reflection enhancing layer 210 is related to the thickness of the film, the pore size of the pores, and the porosity. In addition, the ratio of the deposition times between the metal-based organic hybrid film and the metal oxide film in the deposition process can also have a significant effect on the equivalent refractive index of the pore structure.

As an example of this embodiment, the thickness of the anti-reflection enhancing layer 210 is 10nm to 200nm.

In some examples, the thickness of the anti-reflection enhancing layer 210 may be 10nm, 20nm, 30nm, 40nm, 50nm, 60nm, 70nm, 80nm, 100nm, 120nm, 150nm, 200nm, or the thickness of the anti-reflection enhancing layer 210 may be between any two of the above.

As an example of this embodiment, the aperture of the aperture in the anti-reflection enhancing layer 210 is 1nm to 30nm.

In some examples, the pore size of the pores in the anti-reflection enhancing layer 210 is about 1nm, 2nm, 3nm, 5nm, 7nm, 10nm, 12nm, 14nm, 15nm, 17nm, 20nm, 25nm, 30nm, or the pore size of the pores in the anti-reflection enhancing layer 210 may be between any two of the pore sizes described above.

As an example of this embodiment, the porosity of the anti-reflection enhancing layer 210 is 10% -70%.

In some examples, the porosity of the anti-reflection enhancing layer 210 is 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, or the porosity of the anti-reflection enhancing layer 210 may be between any two of the above.

As an example of this embodiment, the material of the metal-based organic hybrid film includes one or more of an aluminum-based hydroquinone hybrid material, a zinc-based hydroquinone hybrid material, and a titanium-based hydroquinone hybrid material.

As an example of this embodiment, a metal-based organic hybrid film is prepared by deposition of a molecular layer.

As an example of this embodiment, the material of the metal oxide film includes one or more of aluminum oxide, zinc oxide, and titanium oxide.

As an example of this embodiment, a metal oxide film is prepared by atomic layer deposition.

As an example of this embodiment, the metal element in the metal oxide film is the same as the metal element in the metal-based organic hybrid film. This is advantageous in that the metal oxide film and the metal-based organic hybrid film are more tightly combined, and the stability of the laminated structure is enhanced.

It is understood that the process of molecular layer deposition and atomic layer deposition each involve multiple deposition cycles.

As an example of this embodiment, the ratio between the number of deposition cycles of the metal-based organic hybrid film and the number of deposition cycles of the metal oxide film may be 1 (1 to 5).

In some examples, the ratio between the number of deposition cycles of the metal-based organic hybrid film and the number of deposition cycles of the metal oxide film may be 1:1, 1:2, 1:3, 1:4, 1:5, or the ratio of the number of deposition cycles of both may be between any two of the ratios described above. As this ratio increases, the pore size and porosity in the resulting laminate structure also decreases, thereby obtaining an antireflection reinforcing layer 210 having a higher equivalent refractive index.

In the above embodiments, the antireflection device may be an optical device.

As some examples, the optical device may be an imaging device, such as a display, the substrate of which includes a panel glass, and the anti-reflective film layer structure may be disposed on the panel glass of the display.

As some examples, the optical device may be a projection apparatus, such as a projector, the substrate of which includes a lens, and the anti-reflective film layer structure may be disposed on the lens of the projector.

As some examples, the optics may also include an image capturing device, such as a camera, the substrate of which includes a lens, and the anti-reflective film layer structure may be disposed on the lens.

In a first aspect, the present disclosure further provides a method for manufacturing an anti-reflection device, where the method includes the following steps S1 to S3.

Step S1, providing a substrate.

As an example of this embodiment, the substrate may be a workpiece carrying the anti-reflective film layer structure. The workpiece may be, but is not limited to, an optical lens. The material of the optical lens can be organic glass or inorganic glass.

And S2, preparing an anti-reflection base layer on the substrate.

As an example of this embodiment, the step of preparing an anti-reflection base layer on the substrate includes:

As an example of this embodiment, the material of the high refractive index film includes one or more of titanium oxide, aluminum oxide, tantalum oxide, and zirconium oxide.

As an example of this embodiment, the material of the low refractive index film includes one or more of silicon oxide and magnesium fluoride.

It will be appreciated that the materials, layers, etc. of the high refractive index film and the low refractive index film may be set according to specific requirements.

As an example of this embodiment, the method of preparing the high refractive index film may be a physical vapor deposition method or an atomic layer deposition method.

As an example of this embodiment, the method of preparing the low refractive index film may be a physical vapor deposition method or an atomic layer deposition method.

And step S3, placing the substrate in a deposition chamber, and preparing the anti-reflection enhancement layer on the substrate.

Wherein the step of preparing the anti-reflection enhancing layer comprises: depositing to form the metal-based organic hybrid film with a porous structure.

As an example of this embodiment, the metal-based organic hybrid material is deposited by molecular layer deposition.

In this example, the step of depositing to form the metal-based organic hybrid film includes: and introducing a first metal precursor into the deposition chamber and attaching the first metal precursor to the substrate to form a first monolayer, and introducing an organic precursor into the deposition chamber and attaching the organic precursor to the substrate to form a second monolayer. Wherein the step of forming the first monolayer and the step of forming the second monolayer are integrated as a single first deposition cycle. It will be appreciated that each deposition cycle is capable of forming a layer of metal-based organic hybrid material, with multiple deposition cycles being performed in succession to form a continuous layer of metal-based organic hybrid film.

In this example, the first metal precursor is selected from one or more of trimethylaluminum, ethylene-di-zinc, and titanium tetrachloride, and the organic precursor is selected from hydroquinone.

As an example of this embodiment, the number of first deposition cycles is 40 to 500. It will be appreciated that the number of first deposition cycles is related to the thickness of the metal-based organic hybrid film, the greater the number of first deposition cycles, the thicker the thickness of the metal-based organic hybrid film. Also, the number of first deposition cycles is related to the pore structure in the metal-based organic hybrid film. In general, both the porosity and pore size in metal-based organic hybrid membranes exhibit a tendency to increase significantly and then decrease slightly as the number of first deposition cycles increases.

In some examples, the number of first deposition cycles may be 40, 60, 80, 100, 120, 150, 200, 250, 300, 400, 500, or the number of first deposition cycles may be between any two of the above.

As an example of this embodiment, the step of purging the deposition chamber may be included after each first monolayer is formed and after each second monolayer is formed. The step of purging the deposition chamber includes: a protective gas is introduced into the deposition chamber to remove unreacted materials and byproducts of the reaction. This helps to ensure the purity of the surface of the previously produced material to ensure continued deposition.

As an example of this embodiment, in the step of depositing the metal-based organic hybrid film, the temperature of the deposition chamber is controlled to 150 ℃ to 300 ℃. Experiments prove that the temperature of the deposition chamber can influence the aperture and the porosity of the formed metal-based organic hybrid film, and the control of the temperature of the deposition chamber to 150-300 ℃ is beneficial to obtaining the metal-based organic hybrid film with more proper aperture and porosity.

In some examples, in the step of depositing the metal-based organic hybrid film, the temperature of the deposition chamber may be controlled to 150 ℃, 170 ℃, 200 ℃, 220 ℃, 250 ℃, 270 ℃, 300 ℃, or the temperature of the deposition chamber may also be controlled to be between any two of the above temperatures.

It will be appreciated that if the anti-reflection enhancing layer is a metal-based organic hybrid film, the preparation of the anti-reflection enhancing layer can be accomplished by the above steps.

As a further example of this embodiment, the step of preparing the anti-reflection enhancing layer further includes depositing a metal oxide film, and the step of depositing a metal-based organic hybrid film and the step of depositing a metal oxide film are alternately performed.

In this example, the manner of depositing the metal oxide film may be an atomic layer deposition method. The atomic layer deposition mode is adopted, so that the metal oxide film can be uniformly attached to the hole wall of the metal-based organic hybrid film prepared in advance, and the continuity of the preparation process between the metal-based organic hybrid film and the metal oxide film is improved.

As an example of this embodiment, the step of depositing the metal-based organic hybrid film and the step of depositing the metal oxide film may be sequentially performed in the same deposition chamber.

As an example of this embodiment, the step of depositing a metal oxide film includes: a second metal precursor is introduced into the deposition chamber and attached to the substrate to form a third monolayer. An oxidizing agent is introduced into the deposition chamber and is attached to the substrate to form a fourth monolayer. The second deposition cycle is repeated a plurality of times with the step of forming the third monolayer and the step of forming the fourth monolayer taken as a whole as a single second deposition cycle.

Wherein, at least one first deposition cycle is continuously carried out to form a metal-based organic hybrid film, at least one second deposition cycle is continuously carried out to form a metal oxide film, and at least one metal-based organic hybrid film and at least one metal oxide film are alternately formed. It is understood that the alternation is capable of forming at least one metal-based organic hybrid film and at least one metal oxide film. Each of the metal-based organic hybrid films may have a porous structure therein.

In this example, the first deposition cycle may be performed only once when each layer of the metal-based organic hybrid film is formed. Accordingly, after each first deposition cycle is performed to form each metal-based organic hybrid film, one or more second deposition cycles may be performed in succession to form one metal oxide film. It will be appreciated that in other examples, the first deposition cycle may also be performed a plurality of times in succession as each layer of metal-based organic hybrid film is formed.

In this example, the second metal precursor is selected from one or more of trimethylaluminum, ethylene zinc, and titanium tetrachloride. In a further example, the first metal precursor and the second metal precursor are selected from the same material.

Wherein the oxidizing agent may be selected from one or more of ozone and water.

As an example of this embodiment, in the step of depositing the metal oxide film, the temperature of the deposition chamber is controlled to 150 ℃ to 300 ℃.

In some examples, in the step of depositing the metal oxide film, the temperature of the deposition chamber may be controlled to 150 ℃, 170 ℃, 200 ℃, 220 ℃, 250 ℃, 270 ℃,300 ℃, or the temperature of the deposition chamber may also be controlled to be between any two of the above temperatures.

It will be appreciated that if the anti-reflection enhancing layer comprises a metal-based organic hybrid film and a metal oxide film attached to the walls of the holes thereof, the preparation of the anti-reflection enhancing layer can be accomplished by the above steps.

As an example of this embodiment, the ratio of the number of times the first deposition cycle is performed to the number of times the second deposition cycle is performed is 1 (1-5).

In some examples, the ratio of the number of times the first deposition cycle is performed to the number of times the second deposition cycle is performed may be 1:1, 1:2, 1:3, 1:4, 1:5, or the ratio of the number of deposition cycles of both may be between any two of the ratios described above.

As a further example of this embodiment, each time the metal-based organic hybrid film and the subsequent metal oxide film are formed, the ratio of the number of times the first deposition cycle is performed to the number of times the second deposition cycle is performed is 1 (1 to 5).

Further, the disclosure also provides an application of the metal-based organic hybrid film in an antireflection film layer structure. The antireflection film layer structure comprises an antireflection enhancement layer, the antireflection enhancement layer comprises a metal-based organic hybrid film, and the metal-based organic hybrid film has a porous structure.

In this embodiment, the metal-based organic hybrid film is the metal-based organic hybrid film described in any of the embodiments above.

As an example of this embodiment, the equivalent refractive index of the entire anti-reflection enhancing layer is 1.2 to 1.5.

As an example of this embodiment, the thickness of the anti-reflection enhancing layer is 10nm to 200nm.

As an example of this embodiment, the aperture of the aperture in the antireflection enhancement layer is 1nm to 30nm.

As an example of this embodiment, the porosity of the anti-reflection enhancing layer is 10% -70%.

The preparation raw materials of the metal-based organic hybrid film comprise a first metal precursor and an organic precursor; wherein,

As an example of this embodiment, the first metal precursor is selected from one or more of trimethylaluminum, ethylene-di-zinc, and titanium tetrachloride, and the organic precursor is selected from hydroquinone.

The present disclosure also provides the following examples to further illustrate some implementations of the above preparation methods. Accordingly, the present disclosure also provides the following comparative examples to illustrate the advantages of this preparation method.

Example 1.1

Using K9 glass as a substrate, the substrate was placed in a deposition chamber of a molecular layer deposition apparatus.

Preparing a metal-based organic hybrid film: the temperature in the deposition chamber was controlled at 200 ℃, trimethylaluminum was used as the metal precursor, and hydroquinone was used as the organic precursor. The single deposition cycle is: and 2s of trimethylaluminum is introduced into the deposition chamber, argon is introduced into the deposition chamber to purge for 30s, 3s of hydroquinone is introduced into the deposition chamber, argon is introduced into the deposition chamber to purge for 60s, and the flow rate of all gases is controlled to be 2000sccm. And carrying out 250 deposition cycles to form the metal-based organic hybrid film serving as an anti-reflection enhancement layer.

Example 1.2

Example 1.2 differs from example 1.1 only in that: in the step of preparing the metal-based organic hybrid film, 50 deposition cycles were performed.

Example 1.3

Example 1.3 differs from example 1.1 only in that: in the step of preparing the metal-based organic hybrid film, 100 deposition cycles were performed.

Example 1.4

Example 1.4 differs from example 1.1 only in that: in the step of preparing the metal-based organic hybrid film, 500 deposition cycles were performed.

Example 1.5

Example 1.5 differs from example 1.1 only in that: in the step of preparing the metal-based organic hybrid film, the temperature in the deposition chamber is controlled to 150 ℃.

Example 1.6

Example 1.6 differs from example 1.1 only in that: in the step of preparing the metal-based organic hybrid film, the temperature in the deposition chamber is controlled to 250 ℃.

Example 1.7

Example 1.7 differs from example 1.1 only in that: in the step of preparing the metal-based organic hybrid film, the temperature in the deposition chamber is controlled to 300 ℃.

Example 1.8

Example 1.8 differs from example 1.1 only in that: the preparation method of the metal-based organic hybrid film further comprises the step of preparing a metal oxide film, wherein the process comprises the following steps of: the temperature in the deposition chamber was controlled to 200 ℃, trimethylaluminum was used as the metal precursor, and water was used as the oxidant. The single deposition cycle is: and 2s of trimethylaluminum is introduced into the deposition chamber, argon is introduced into the deposition chamber to purge for 30s, 3s of water vapor is introduced into the deposition chamber, argon is introduced into the deposition chamber to purge for 60s, and the flow rate of all gases is controlled to be 2000sccm. The number of deposition cycles of the metal-based organic hybrid film is 250, and each time 1 deposition cycle of the metal-based organic hybrid film is performed, 1 deposition cycle of the metal oxide film is performed immediately, and the formed metal-based organic hybrid film and the metal oxide film are integrally used as an antireflection enhancement layer.

Example 1.9

Example 1.9 differs from example 1.8 only in that: each deposition cycle of the metal-based organic hybrid film was followed by 2 deposition cycles of the metal oxide film.

Example 1.10

Example 1.10 differs from example 1.8 only in that: each deposition cycle of the metal-based organic hybrid film was followed by 5 deposition cycles of the metal oxide film.

Example 1.11

Example 1.11 differs from example 1.8 only in that: each deposition cycle of the metal-based organic hybrid film was followed by 10 deposition cycles of the metal oxide film.

Example 1.12

Example 1.12 differs from example 1.8 only in that: in the step of preparing the metal-based organic hybrid film, diethyl zinc is adopted as a metal precursor; in the step of preparing the metal oxide film, diethyl zinc is used as a metal precursor.

Example 1.13

Example 1.13 differs from example 1.8 only in that: in the step of preparing the metal-based organic hybrid film, titanium tetrachloride is adopted as a metal precursor; in the step of preparing the metal oxide film, titanium tetrachloride is used as a metal precursor.

Test 1: the thickness, pore diameter, porosity and equivalent refractive index of each of the antireflection reinforcing layers prepared in examples 1.1 to 1.11 were measured, and the results are shown in table 1.

TABLE 1

The terms "to" in Table 1 represent submultiples.

As can be seen from table 1, parameters such as aperture and porosity of the anti-reflection enhancing layer in the disclosure can be correspondingly controlled by deposition times, deposition temperatures, and metal oxide films with different thicknesses stacked in the preparation process, which is beneficial to forming anti-reflection enhancing layers with different equivalent refractive indexes, thereby realizing preparation of an anti-reflection enhancing layer with variable refractive index. In general, as the deposition cycle increases, the thickness of the metal-based organic hybrid membrane gradually increases, and the pore size and porosity show a tendency to increase first and then decrease slightly. The change trend of the equivalent refractive index is opposite to the change trend of the pore diameter and the porosity, and the trend of decreasing before increasing is presented. As the deposition temperature increases, pore size and porosity exhibit a tendency to slightly increase followed by a slight decrease, and correspondingly the equivalent refractive index exhibits a tendency to slightly decrease followed by a slight increase.

For example, referring to table 1, in the steps of preparing metal-based organic hybrid membranes of examples 1.1 to 1.4, the number of deposition cycles is different, and accordingly, the thickness, pore size and porosity of the prepared metal-based organic hybrid membranes are also different. The number of deposition cycles for example 1.1 is greater than for examples 1.2 and 1.3, with a correspondingly higher porosity, pore size and lower equivalent refractive index for example 1.1. The number of deposition cycles was higher for example 1.4 than for example 1.1, but the porosity and pore size were slightly lower for example 1.4 and the equivalent refractive index was slightly higher than for example 1.1. This may be due to the fact that the metal-based organic hybrid material deposited later may cause some blockage of the holes when the deposition cycles are excessive.

Referring to table 1, the deposition temperatures in the steps of preparing the metal-based organic hybrid film were different in examples 1.1 and 1.5 to 1.7. The deposition temperature of example 1.5 was only 150 c, with significantly lower pore size and porosity. The deposition temperature for example 1.6 was 250 c, which is closer to example 1.1 in pore size and porosity. The deposition temperature of example 1.7 was further increased to 300 c and the pore size and porosity were also significantly lower than in example 1.1.

Referring to table 1, a metal oxide film was also prepared in examples 1.8 to 1.11, compared with example 1.1. As the deposition amount of the metal oxide film increases, the pore diameter of the entire antireflection reinforcing layer gradually decreases, and the porosity also gradually decreases. The equivalent refractive index gradually increases accordingly. The antireflection enhancing layer prepared in example 1.11 gradually approaches the refractive index of the alumina crystal material as a whole, at which time the antireflection enhancing layer has substantially lost the porous structure and also has substantially no effect of enhancing the antireflection effect.

Example 2.1

Adopting K9 glass as a substrate, sequentially adopting ethanol and ultrapure water for ultrasonic cleaning, and then drying for later use.

Preparing an antireflection base layer: placing a substrate in a deposition chamber, and sequentially depositing the following films by adopting an atomic layer deposition mode:

(1) Titanium dioxide film with thickness of 12.5nm and refractive index of 2.31;

(2) A silica film having a thickness of 89nm and a refractive index of 1.45.

An anti-reflection enhancing layer as in example 1.1 was prepared on the surface of the anti-reflection base layer.

Example 2.2

(1) An alumina film having a thickness of 12.5nm and a refractive index of 1.62;

(2) A silica film having a thickness of 44nm and a refractive index of 1.45;

(3) Titanium dioxide film with thickness of 2.8nm and refractive index of 2.31;

(4) A silica film having a thickness of 42nm and a refractive index of 1.45.

An anti-reflection enhancing layer as in example 1.8 was prepared on the surface of the anti-reflection base layer.

Example 2.3

(1) A silica film having a thickness of 110nm and a refractive index of 1.45;

(2) Titanium dioxide film with thickness of 10.5nm and refractive index of 2.31;

(3) A silica film having a thickness of 35.5nm and a refractive index of 1.45;

(4) A titanium dioxide film with the thickness of 113nm and the refractive index of 2.31;

(5) A silica film having a thickness of 43nm and a refractive index of 1.45;

(6) A titanium dioxide film with a thickness of 21nm and a refractive index of 2.31;

(7) A silica film having a thickness of 42nm and a refractive index of 1.45;

(8) Titanium dioxide film with thickness of 108nm and refractive index of 2.31;

(9) A magnesium fluoride film with a thickness of 87.5nm and a refractive index of 1.38.

Comparative example 1

Comparative example 1 differs from example 2.1 only in that comparative example 1 does not prepare an antireflection enhancing layer.

Comparative example 2

Comparative example 2 differs from example 2.2 only in that comparative example 2 does not prepare an antireflection enhancing layer.

Comparative example 3

Comparative example 3 differs from example 2.3 only in that comparative example 3 does not prepare an antireflection enhancing layer.

Test 2: the coated glasses of examples 2.1, 2.2 and 3 were tested for reflectivity for 400nm to 800nm bands, and the results are shown in Table 2. Fig. 3 shows a graph of reflectance of the coated glass according to wavelength in comparative example 3, and fig. 4 shows a graph of reflectance of the coated glass according to wavelength in examples 2.1 and 2.2.

TABLE 2

No anti-reflection enhancing layer was prepared for each of comparative examples 1 to 3. Referring to table 2, the average reflectance of the coated glass showed a gradual decrease trend as the number of film layers in the antireflection base layer increased, but even with the antireflection base layer composed of 9 film layers, the average reflectance of the coated glass still reached 0.53%. As shown in connection with fig. 3, the coated glass of comparative example 3 has a reflectance of substantially less than 1%, but still has a transmittance of 0.5% or more for light in a partial wavelength band.

The antireflection enhancement layers in the present disclosure were also prepared in examples 2.1 to 2.3, compared to comparative examples 1 to 3. Referring to Table 2, the average reflectance of the coated glasses of examples 2.1 to 2.3 were significantly reduced compared to comparative examples 1 to 3. More importantly, even the simpler antireflective base layers of examples 2.1 and 2.2 still exhibited lower reflectivity than the more complex antireflective base layer structure of comparative example 3. As shown in fig. 4, the reflectivity of the coated glass of each of examples 2.1 and 2.2 was lower than 0.2%. The above results all show that the anti-reflection coated glass disclosed by the disclosure can ensure lower reflectivity and simplify the anti-reflection film layer structure.

Note that the above embodiments are for illustrative purposes only and are not meant to be limiting herein.

It should be understood that the steps are not strictly limited to the order of execution unless explicitly recited herein, and the steps may be executed in other orders. Moreover, at least a portion of the steps in the preparation process may include a plurality of sub-steps or stages, which are not necessarily performed at the same time, may be performed at different times, may not necessarily be performed sequentially, and may be performed alternately or alternately with at least a portion of the sub-steps or stages of other steps or other steps.

In this specification, each embodiment is described in a progressive manner, and each embodiment is mainly described by differences from other embodiments, and identical and similar parts between the embodiments are all enough to be referred to each other.

The technical features of the above embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.

Claims

1. The anti-reflection device is characterized by comprising a substrate and an anti-reflection film layer structure which is arranged on the substrate in a laminated mode, wherein the anti-reflection film layer structure comprises an anti-reflection base layer and an anti-reflection enhancement layer which is arranged on the anti-reflection base layer in a laminated mode, and the anti-reflection enhancement layer comprises a metal-based organic hybrid film with a porous structure.

2. The anti-reflective device of claim 1 wherein the anti-reflective enhancement layer is the metal-based organic hybrid film; or alternatively

3. The antireflection device of claim 2 wherein the material of the metal oxide film comprises one or more of aluminum oxide, zinc oxide, and titanium oxide.

4. The device of claim 1, wherein the anti-reflection enhancement layer has an overall equivalent refractive index of 1.2-1.5.

5. The anti-reflective device of claim 4 wherein the anti-reflective enhancement layer satisfies at least one of the following characteristics:

(1) The thickness of the anti-reflection enhancement layer is 10 nm-200 nm;

(3) The porosity of the anti-reflection enhancement layer is 10% -70%.

6. The antireflection device of any one of claims 1 to 5 wherein the material of the metal-based organic hybrid film comprises one or more of an aluminum-based hydroquinone hybrid material, a zinc-based hydroquinone hybrid material, and a titanium-based hydroquinone hybrid material.

7. The antireflection device of claim 6 wherein the metal-based organic hybrid film is formed by molecular layer deposition.

8. The antireflection device of claim 7 wherein the metal-based organic hybrid film is prepared from a starting material comprising a first metal precursor and an organic precursor; wherein,

9. The antireflection device according to any one of claims 1 to 5 and 7 to 8, wherein the antireflection base layer includes a high refractive index film and a low refractive index film, the high refractive index film having a refractive index higher than that of the low refractive index film;

10. The antireflection device according to claim 9, wherein the total number of film layers of the high refractive index film and the low refractive index film is 2 to 4.

11. The antireflection device of any one of claims 1 to 5, 7 to 8 and 10, wherein the average reflectance of the antireflection film layer structure for light rays in the 400nm to 800nm band is 0.2% or less.

12. A method of making an anti-reflective device comprising the steps of:

Providing a substrate;

Preparing an anti-reflection base layer on the substrate;

13. The method of manufacturing an anti-reflective device according to claim 12, wherein the material of the metal-based organic hybrid film comprises one or more of an aluminum-based hydroquinone hybrid material, a zinc-based hydroquinone hybrid material, and a titanium-based hydroquinone hybrid material.

14. The method of claim 13, wherein the metal-based organic hybrid film is deposited by molecular layer deposition.

15. The method of any one of claims 12 to 14, wherein the step of preparing the anti-reflection enhancing layer further comprises depositing a metal oxide film, and the step of depositing a metal-based organic hybrid film and the step of depositing a metal oxide film are performed alternately.

16. The method of manufacturing an anti-reflective device according to claim 15, wherein the step of depositing the metal-based organic hybrid film comprises: introducing a first metal precursor into a deposition chamber and enabling the first metal precursor to be attached to the substrate to form a first monomolecular layer, and introducing an organic precursor into the deposition chamber and enabling the organic precursor to be attached to the substrate to form a second monomolecular layer;

17. The method of manufacturing an anti-reflective device according to claim 16, wherein the first metal precursor is selected from one or more of trimethylaluminum, ethylzinc, and titanium tetrachloride, and the organic precursor is selected from hydroquinone; and/or the number of the groups of groups,

The second metal precursor is selected from one or more of trimethylaluminum, zinc acetate and titanium tetrachloride, and the oxidant is selected from one or more of water and ozone.

18. The method of manufacturing an anti-reflective device according to claim 16, wherein a ratio of the number of times the first deposition cycle is performed to the number of times the second deposition cycle is performed is 1 (1-5).

19. The method of claim 16, wherein the first deposition cycle is 40-500 times.

20. The method of any one of claims 12 to 14 and 16 to 19, wherein in the step of depositing the metal-based organic hybrid film, the temperature of the deposition chamber is controlled to be 150 ℃ to 300 ℃.

21. The method for manufacturing an antireflection device according to any one of claims 12 to 14 and 16 to 19, wherein the step of manufacturing an antireflection base layer on the substrate comprises:

22. The application of the metal-based organic hybrid film in the antireflection film layer structure is characterized in that the antireflection film layer structure comprises an antireflection enhancement layer, the antireflection enhancement layer comprises the metal-based organic hybrid film, and the metal-based organic hybrid film has a porous structure.

23. The use according to claim 22, wherein the metal-based organic hybrid film constitutes the anti-reflection enhancing layer; or alternatively

24. The use of claim 22, wherein the anti-reflection enhancing layer has an overall equivalent refractive index of 1.2 to 1.5.

25. The use of claim 24, wherein the anti-reflection enhancing layer satisfies at least one of the following characteristics:

(1) The thickness of the anti-reflection enhancement layer is 10 nm-200 nm;

(3) The porosity of the anti-reflection enhancement layer is 10% -70%.

26. The use according to any one of claims 22 to 25, wherein the material of the metal-based organic hybrid film comprises one or more of an aluminium-based hydroquinone hybrid material, a zinc-based hydroquinone hybrid material and a titanium-based hydroquinone hybrid material.

27. The use according to claim 26, wherein the metal-based organic hybrid film is formed by molecular layer deposition.

28. The use according to claim 27, wherein the starting materials for the preparation of the metal-based organic hybrid film comprise a first metal precursor and an organic precursor; wherein,