Optical device, and preparation method therefor and use thereof

Abstract

The present application relates to an optical device, and a preparation method therefor and the use thereof. The optical device comprises a workpiece body and a porous film arranged on the workpiece body, wherein the porous film comprises a porous metal oxide layer or a porous metal-based organic hybrid layer.

Description

Optical device and preparation method and application thereof

[0001] Related applications

[0002] The present application claims priority to the Chinese patent application No. 2024112326458, entitled "Preparation method of porous antireflection film, porous antireflection film and optical device", filed on September 3, 2024, and the Chinese patent application No. 2024112341922, entitled "Antireflection device, preparation method and application of antireflection device", filed on September 3, 2024, the contents of which are hereby incorporated by reference in their entirety. TECHNICAL FIELD

[0003] The present application relates to the field of optical technology, in particular to an optical device and a preparation method and application thereof. BACKGROUND

[0004] Antireflection films are commonly used in optical devices. The antireflection film, also known as an antireflection film, is mainly used to eliminate the reflected light on the surface of devices such as lenses, prisms and plane mirrors, increase the amount of light transmitted by the device, and reduce or eliminate stray light in the system.

[0005] The antireflection film mainly uses the interference cancellation principle of light, and is matched by matching the refractive index of different materials, designing the thickness, and selecting special materials, etc., to achieve the reduction of reflected light and the increase of transmitted light. One of the main features of this optical antireflection film is that if a lower reflectivity is desired, a large number of thin films are often required to form a stacked structure. For example, in some traditional technologies, if the reflectivity of the lens is to be reduced to below 0.5%, a stacked structure composed of more than 9 layers of thin films is required. Therefore, the structure of the antireflection film in the traditional technology is usually complex. SUMMARY

[0006] Therefore, according to various embodiments of the present disclosure, the first aspect provides an optical device, and the technical solution is as follows:

[0007] An optical device, comprising a workpiece body and a porous film arranged on the workpiece body, wherein the porous film comprises a porous metal oxide layer or a porous metal-based organic hybrid layer.

[0008] According to various embodiments of the present disclosure, the second aspect provides a preparation method of an optical device, and the technical solution is as follows:

[0009] A preparation method of an optical device, comprising the following steps:

[0010] Preparation of a porous film, wherein the preparation method of the porous film comprises a molecular deposition method, the porous film comprises a porous metal oxide layer or a porous metal-based organic hybrid layer, and the porous film is used to reduce reflected light on the workpiece body.

[0011] The porous film is disposed on a body of a workpiece.

[0012] According to various embodiments of the present disclosure, a third aspect provides an application of a porous film in an anti-reflective film of an optical device.

[0013] The details of one or more embodiments of the application are set forth in the description below, and other features, objects, and advantages of the application will be apparent from the description and the claims. BRIEF DESCRIPTION OF DRAWINGS

[0014] In order to more clearly illustrate the technical solutions in the embodiments of the present application or in the prior art, the drawings needed to be used in the description of the embodiments or the prior art will be briefly introduced as follows. Obviously, the drawings in the following description only are the embodiments of the present application, and other drawings can be obtained by those skilled in the art without any creative effort on the basis of the disclosed drawings.

[0015] Fig. 1 is a schematic structural diagram of an anti-reflective device according to an embodiment;

[0016] Fig. 2 is a schematic structural diagram of an anti-reflective device according to another embodiment;

[0017] Fig. 3 is a schematic diagram of steps of a method for preparing a porous film;

[0018] Fig. 4 is a photograph of surface topography of two samples in Example 1 before and after the shaping treatment, wherein the left photograph is a photograph of surface topography of the sample before the shaping treatment after standing in air for 20 hours, and the right photograph is a photograph of surface topography of the sample after the shaping treatment after standing in air for 100 hours;

[0019] Fig. 5 is a photograph of surface topography of the samples prepared in Example 1 and Example 14 after being wiped with steel wool, wherein the left photograph is a photograph of surface topography of the sample in Example 1 after being wiped, and the right photograph is a photograph of surface topography of the sample in Example 14 after being wiped;

[0020] Fig. 6 is a photograph of surface topography of the sample in Example 1 observed by a scanning electron microscope;

[0021] Fig. 7 is a photograph of surface topography of the sample in Example 2 observed by a scanning electron microscope;

[0022] Fig. 8 is a photograph of surface topography of the sample in Example 3 observed by a scanning electron microscope;

[0023] Fig. 9 is a curve of transmittance of the sample in Example 1 versus wavelength of incident light, wherein the abscissa is wavelength in nm, and the ordinate is transmittance;

[0024] Figure 10 is a graph of the transmittance of Example 2 as a function of wavelength of incident light, where the abscissa is wavelength in nm and the ordinate is transmittance;

[0025] Figure 11 is a graph of the transmittance of Example 3 as a function of wavelength of incident light, where the abscissa is wavelength in nm and the ordinate is transmittance;

[0026] Figure 12 shows a graph of the reflectance of the coated glass of Comparative Example 4 as a function of wavelength;

[0027] Figure 13 shows a graph of the reflectance of the coated glass of Example 2.1 and Example 2.2 as a function of wavelength.

[0028] Wherein, the reference signs and their meanings are as follows:

[0029] 100, substrate; 110, antireflection enhancement layer; 120, antireflection base layer; 121, high refractive index film; 122, low refractive index film; 200, substrate; 210, antireflection enhancement layer; 220, antireflection base layer; 221, high refractive index film; 222, low refractive index film. DETAILED DESCRIPTION

[0030] For the purposes of this document, a thorough and complete description of the application has been presented. However, the present application can be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and fully convey the scope of the application to those skilled in the art.

[0031] Unless otherwise defined, 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 application belongs. The terminology used in the description of the application herein is for describing particular embodiments only and is not intended to be limiting of the application.

[0032] It should be understood that when an element or layer is referred to as being "on" or "adjacent" or "connected" or "coupled" to another element or layer, it can be directly on, adjacent, connected or coupled to the other element or layer or one or more intervening elements or layers can also be present. In contrast, when an element is referred to as being "directly on," "directly adjacent," "directly connected" or "directly coupled" to another element or layer, there are no intervening elements or layers present. It will be appreciated that, although terms such as first, second, third, etc. can 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 simply used to distinguish one element, component, region, layer or section from another element, component, region, layer or section.

[0033] Spatially relative terms, such as "beneath", "below", "lower", "under", "above", "upper" and the like, can be used herein for ease of description to describe one element or feature's relationship to another element(s) or feature(s) as illustrated in the figures. It will be understood that the spatially relative terms are intended to encompass different orientations of the device in use or operation in addition to the orientations depicted in the figures. For example, if a device in the figures is inverted, then a dependent element or feature described as "below" or "beneath" another element or feature is oriented "above" or "over" the other element or feature. Thus, the exemplary term "below" or "beneath" can encompass both an orientation of above and below. The device can be otherwise oriented (e.g., rotated 90 degrees or at other orientations) and the spatially relative descriptors used herein interpreted accordingly.

[0034] 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 one or more of the associated listed items.

[0035] The anti-reflective film in conventional optical devices usually needs to include multiple thin films, and the refractive index and corresponding thickness and other parameters of the multiple thin films are changed to reduce the reflectivity of light.

[0036] In a first aspect, the present disclosure provides an optical device, comprising a workpiece body and a porous film disposed on the workpiece body, the porous film being configured to reduce reflected light on the workpiece body, the porous film comprising a porous metal oxide layer or a porous metal-based organic hybrid layer.

[0037] It can be understood that the porous film is an anti-reflective film. The anti-reflective film, also known as an anti-reflection film, reduces reflected light.

[0038] The optical device of the present disclosure includes a porous film, which includes a porous metal oxide layer or a porous metal-based organic hybrid layer, and can utilize a microporous structure to reduce the reflection of light at the interface and thus improve the transmittance, and has a simple structure relative to the conventional stacked structure composed of a large number of thin films.

[0039] Experiments have verified that when the porous film includes a porous metal oxide layer, the porous film has excellent anti-reflective effect.

[0040] When the porous film includes the porous metal-based organic hybrid layer, the porous metal-based organic hybrid layer can play the role of the multilayer film in the conventional technology in terms of the reflectance reduction performance.

[0041] As some examples of this embodiment, the porous metal oxide layer has an average light transmittance of 99% or more in the wavelength band of 450 nm to 675 nm.

[0042] As some examples of this embodiment, the porous film including the porous metal oxide layer has an average light transmittance of 99% or more in the wavelength band of 450 nm to 675 nm.

[0043] As some examples of this embodiment, the porous metal oxide layer has a thickness of 40 nm to 100 nm.

[0044] As some examples of this embodiment, the porous metal oxide layer has a pore diameter of 35 nm to 105 nm.

[0045] As some examples of this embodiment, the porous film including the porous metal oxide layer further includes a shape-retaining layer attached to the pore structure of the porous metal oxide layer.

[0046] In this embodiment, the shape-retaining layer covers the surface of the porous metal oxide layer. It is understood that the surface of the porous metal oxide layer is porous, and the shape-retaining layer can be attached to the pore walls therein. The shape-retaining layer can reinforce the pore structure of the porous metal oxide layer, so that the porous metal oxide layer can maintain the pore structure when subjected to external forces such as friction. Moreover, the shape-retaining layer enables the porous metal oxide layer to be stably attached to the substrate.

[0047] As some examples of this embodiment, the material of the shape-retaining layer is selected from oxides. The oxides have a similar material structure to the porous metal oxide layer, which enables the shape-retaining layer to be more tightly combined with the porous metal oxide layer.

[0048] In this example, the material of the shape-retaining layer can be selected from one or more of titanium dioxide, aluminum oxide, and silicon dioxide.

[0049] In this example, the material of the shape-retaining layer is the same as the material of the porous metal oxide layer.

[0050] As some examples of this embodiment, the thickness of the shape-retaining layer is ≤ 10 nm. The use of a shape-retaining layer with a thickness of less than 10 nm can avoid the shape-retaining layer filling the pore structure as much as possible and maintaining the original pore structure of the porous metal oxide layer. Optionally, the thickness of the shape-retaining layer can be 1 nm to 3 nm. This is conducive to obtaining good shape-retaining performance while substantially not changing the pore structure.

[0051] In this example, the thickness of the shape-preserving layer can be 1 nm, 1.5 nm, 2 nm, 2.5 nm, 3 nm, or the thickness of the shape-preserving layer can also be between any two thicknesses described above.

[0052] As some examples of this embodiment, the way of preparing the shape-preserving layer on the porous metal oxide layer is selected from one or more of chemical vapor deposition (CVD), physical vapor deposition (PVD), atomic layer deposition (ALD), molecular layer deposition, and liquid phase epitaxy. More preferably, atomic layer deposition is used to prepare the shape-preserving layer to form a thinner and more uniform shape-preserving layer, which provides better shape-preserving ability while minimizing the impact on light transmission performance.

[0053] As some examples of this embodiment, a porous film includes a porous metal oxide layer and a shape-preserving layer attached to the pore walls of the porous metal oxide layer.

[0054] As some examples of this embodiment, the average light transmittance of the porous film in the 450 nm to 675 nm wavelength band is 99% or more.

[0055] As some examples of this embodiment, the thickness of the porous metal oxide layer is 40 nm to 100 nm.

[0056] As some examples of this embodiment, the pore size of the pores in the porous metal oxide layer is 35 nm to 105 nm.

[0057] As some examples of this embodiment, the porous metal-based organic hybrid layer is prepared by molecular layer deposition.

[0058] In at least some embodiments of the present disclosure, the porous metal-based organic hybrid layer can be prepared by molecular layer deposition, and the desired porous structure can be directly formed during the deposition process. Compared with the traditional design of multi-layer thin films, the use of the porous metal-based organic hybrid layer to participate in the composition of the anti-reflective structure makes the overall process simpler, with lower process difficulty and easier implementation.

[0059] In addition, the porous metal-based organic hybrid layer can be prepared by molecular layer deposition. By controlling the temperature and thickness of the porous metal-based organic hybrid layer during the deposition process, or by superimposing other metal oxide layers on the pore wall surface of the porous metal-based organic hybrid layer, the porosity and pore distribution can be adjusted, so that the refractive index of the porous metal-based organic hybrid layer is adjustable. This is beneficial to broaden the application range of the porous metal-based organic hybrid layer, so that it can form a low reflectivity anti-reflective structure with a variety of different anti-reflective base layers.

[0060] It can be understood that the refractive index of the porous metal-based organic hybrid layer can gradually change along the thickness direction, but the porous metal-based organic hybrid layer as a whole has an equivalent refractive index. As an example of this embodiment, the equivalent refractive index of the porous metal-based organic hybrid layer is 1.2-1.5.

[0061] Further, in this embodiment, the equivalent refractive index of the porous metal-based organic hybrid layer is 1.23-1.3. The porous metal-based organic hybrid layer with an equivalent refractive index in this range can achieve a significantly better effect of enhanced antireflection, which is conducive to obtaining an antireflection structure with a significantly lower reflectivity.

[0062] In some examples, the equivalent refractive index of the porous metal-based organic hybrid layer can be 1.23, 1.24, 1.25, 1.26, 1.27, 1.28, 1.29, 1.3, or the equivalent refractive index of the porous metal-based organic hybrid layer can also be between any two refractive indices described above.

[0063] In general, the equivalent refractive index of the porous metal-based organic hybrid layer is related to factors such as the thickness of the film, the pore size of the pores, and the porosity.

[0064] As an example of this embodiment, the thickness of the porous metal-based organic hybrid layer is 10-200 nm.

[0065] In some examples, the thickness of the porous metal-based organic hybrid layer can be 10 nm, 20 nm, 30 nm, 40 nm, 50 nm, 60 nm, 70 nm, 80 nm, 100 nm, 120 nm, 150 nm, 200 nm, or the thickness of the porous metal-based organic hybrid layer can also be between any two thicknesses described above.

[0066] As an example of this embodiment, the pore size of the pores in the porous metal-based organic hybrid layer is 1-30 nm.

[0067] In some examples, the pore size of the pores in the porous metal-based organic hybrid layer is about 1 nm, 2 nm, 3 nm, 5 nm, 7 nm, 10 nm, 12 nm, 14 nm, 15 nm, 17 nm, 20 nm, 25 nm, 30 nm, or the pore size of the pores in the porous metal-based organic hybrid layer can also be between any two pore sizes described above.

[0068] As an example of this embodiment, the porosity of the porous metal-based organic hybrid layer is 10-70%.

[0069] In some examples, the porosity of the porous metal-based organic hybrid layer is 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, or the porosity of the porous metal-based organic hybrid layer can also be between any two of the above porosities.

[0070] As an example of this embodiment, the material of the porous metal-based organic hybrid layer includes one or more of an aluminum-based hydroquinone hybrid material, a zinc-based hydroquinone hybrid material, and a titanium-based hydroquinone hybrid material. Among them, 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 can be obtained by reacting a zinc compound with hydroquinone, and the zinc compound can include but is not limited to diethylzinc. The titanium-based hydroquinone hybrid material can be obtained by reacting a titanium compound with hydroquinone, and the titanium compound can include but is not limited to titanium tetrachloride.

[0071] As an example of this embodiment, the porous metal-based organic hybrid layer is formed by molecular layer deposition. In the process of molecular layer deposition, a porous structure can be directly formed in the porous metal-based organic hybrid layer formed. By controlling the conditions such as the temperature and the number of deposition cycles in the deposition process, the porous structure in the porous metal-based organic hybrid layer can be correspondingly controlled.

[0072] As an example of this embodiment, the raw material for preparing the porous metal-based organic hybrid layer includes a first metal precursor and an organic precursor. Among them, the first metal precursor is selected from one or more of trimethylaluminum, diethylzinc, and titanium tetrachloride, and the organic precursor is selected from hydroquinone.

[0073] It can be understood that the material of the porous metal-based organic hybrid layer is related to the raw material for preparing the same. For example, if the material of the porous metal-based organic hybrid layer includes an aluminum-based hydroquinone hybrid material, the first metal precursor can be trimethylaluminum, and the organic precursor can be hydroquinone. If the material of the porous metal-based organic hybrid layer includes a zinc-based hydroquinone hybrid material, the first metal precursor can be diethylzinc, and the organic precursor can be hydroquinone. If the material of the porous metal-based organic hybrid layer includes a titanium-based hydroquinone hybrid material, the first metal precursor can be titanium tetrachloride, and the organic precursor can be hydroquinone.

[0074] As an example of this embodiment, the porous film includes the porous metal-based organic hybrid layer, and the porous metal-based organic hybrid layer constitutes an antireflection enhancement layer.

[0075] As another example of this embodiment, the porous film includes the porous metal-based organic hybrid layer, and further includes a metal oxide layer, a material of the metal oxide layer includes a metal oxide, the porous metal-based organic hybrid layer and the metal oxide layer constitute the antireflection enhancement layer, a number of layers of the porous metal-based organic hybrid layer and the metal oxide layer is at least one, and the porous metal-based organic hybrid layer and the metal oxide layer are alternately stacked. It can be understood that each layer of the porous metal-based organic hybrid layer can have a porous structure, and each layer of the metal oxide layer can be attached to the pore wall surface of the immediately adjacent porous metal-based organic hybrid layer.

[0076] As an example of this embodiment, the equivalent refractive index of the antireflection enhancement layer as a whole is 1.2-1.5. That is, the equivalent refractive index of the stacked structure composed of the porous metal-based organic hybrid layer and the metal oxide layer of this embodiment is 1.2-1.5.

[0077] Further, in this embodiment, the equivalent refractive index of the antireflection enhancement layer is 1.23-1.3. The antireflection enhancement layer having an equivalent refractive index in this range can achieve a significantly better effect of enhancing antireflection, and is advantageous in obtaining an antireflection structure having a significantly lower reflectance.

[0078] In some examples, the equivalent refractive index of the antireflection enhancement layer can be 1.23, 1.24, 1.25, 1.26, 1.27, 1.28, 1.29, 1.3, or the equivalent refractive index of the antireflection enhancement layer can also be between any two of the above refractive indices.

[0079] Overall, the equivalent refractive index of the antireflection enhancement layer is related to factors such as the thickness of the film, the pore diameter of the pores, and the porosity. In addition, the ratio of the number of depositions between the porous metal-based organic hybrid layer and the metal oxide layer during the deposition process also has a significant impact on the equivalent refractive index of the pore structure.

[0080] As an example of this embodiment, the thickness of the antireflection enhancement layer is 10-200 nm.

[0081] In some examples, the thickness of the antireflection enhancement layer can be 10 nm, 20 nm, 30 nm, 40 nm, 50 nm, 60 nm, 70 nm, 80 nm, 100 nm, 120 nm, 150 nm, 200 nm, or the thickness of the antireflection enhancement layer 210 can also be between any two of the above thicknesses.

[0082] As an example of this embodiment, the pore diameter of the pores in the antireflection enhancement layer is 1-30 nm.

[0083] In some examples, the pore size of the pores in the antireflection enhancement layer is about 1 nm, 2 nm, 3 nm, 5 nm, 7 nm, 10 nm, 12 nm, 14 nm, 15 nm, 17 nm, 20 nm, 25 nm, 30 nm, or the pore size of the pores in the antireflection enhancement layer can also be between any two of the above.

[0084] As an example of this embodiment, the porosity of the antireflection enhancement layer is 10% to 70%.

[0085] As an example of this embodiment, the porosity of the antireflection enhancement layer is 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, or the porosity of the antireflection enhancement layer can also be between any two of the above.

[0086] As an example of this embodiment, the material of the metal oxide layer includes one or more of aluminum oxide, zinc oxide, and titanium oxide.

[0087] As an example of this embodiment, the metal oxide layer is formed by atomic layer deposition.

[0088] As an example of this embodiment, the metal element in the metal oxide layer is the same as the metal element in the porous metal-based organic hybrid layer. This facilitates the metal oxide layer to be more closely combined with the porous metal-based organic hybrid layer, enhancing the stability of the stacked structure.

[0089] It can be understood that the processes of molecular layer deposition and atomic layer deposition both include multiple deposition cycles.

[0090] As an example of this embodiment, the ratio between the number of deposition cycles of the porous metal-based organic hybrid layer and the number of deposition cycles of the metal oxide layer can be 1: (1-5).

[0091] In some examples, the ratio between the number of deposition cycles of the porous metal-based organic hybrid layer and the number of deposition cycles of the metal oxide layer can be 1:1, 1:2, 1:3, 1:4, 1:5, or the ratio between the number of deposition cycles of the two can also be between any two of the above. As the ratio increases, the pore size and porosity in the formed stacked structure also decrease, thereby obtaining an antireflection enhancement layer with a higher equivalent refractive index.

[0092] As an example of this embodiment, the porous film further includes an antireflection base layer, the antireflection base layer and the antireflection enhancement layer are stacked, and the antireflection base layer and the antireflection enhancement layer form an antireflection structure.

[0093] As an example of this embodiment, the average reflectivity of the antireflection structure for light in the 400 nm to 800 nm wavelength band is below 0.2%.

[0094] It can be understood that the antireflection base layer can refer to the film layer with antireflection effect known in the present disclosure. As an example of the embodiment, the antireflection base layer includes a high refractive index film and a low refractive index film, the refractive index of the high refractive index film is higher than the refractive index of 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 stacked. Through the structure of the stacked design of the high refractive index film and the low refractive index film, the reflectivity of the substrate where it is located can be reduced.

[0095] As an example of the embodiment, 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 stacked. It can be understood that as the number of layers of the high refractive index film and the low refractive index film increases, the antireflection effect of the antireflection base layer composed of the high refractive index film and the low refractive index film can also be enhanced, but this also increases the structural complexity of the antireflection base layer, and correspondingly makes the preparation process more complex.

[0096] As an example of the embodiment, the number of high refractive index films and low refractive index films is the same, and in the antireflection base layer, the high refractive index film closest to the substrate is arranged, and the low refractive index film closest to the antireflection enhancement layer is arranged.

[0097] In some examples, the total number of layers of the high refractive index film and the low refractive index film is 2-4 layers, which is beneficial to simplify the structure of the antireflection base layer as much as possible. And as will be explained below, even for the antireflection base layer with a simple structure in this example, by corresponding arrangement of the antireflection enhancement layer, the overall antireflection structure can still have a significantly lower reflectivity.

[0098] As an example of the embodiment, the porous film further includes a substrate, and the antireflection structure is stacked on the substrate.

[0099] As an example of the embodiment, the optical device can be an imaging device, such as a display, the workpiece body of the display includes a panel glass, and the porous film can be arranged on the panel glass of the display.

[0100] As an example of the embodiment, the optical device can be a projection device, such as a projector, the workpiece body of the projector includes a lens, and the porous film can be arranged on the lens of the projector.

[0101] As an example of the embodiment, the optical device can further include a camera device, such as a camera, the workpiece body of the camera includes a lens, and the porous film can be arranged on the lens.

[0102] In the above embodiments, the optical device can be an antireflection device.

[0103] The present disclosure provides an anti-reflective device, which comprises a substrate and an anti-reflective structure stacked on the substrate, the anti-reflective structure comprising an anti-reflective enhancement layer, the anti-reflective enhancement layer comprising a porous metal-based organic hybrid layer.

[0104] The present disclosure provides an anti-reflective device, which comprises a substrate and an anti-reflective structure stacked on the substrate, the anti-reflective structure comprising an anti-reflective enhancement layer, the anti-reflective enhancement layer comprising a porous metal-based organic hybrid layer.

[0105] The present disclosure provides an anti-reflective device, which comprises a substrate and an anti-reflective structure stacked on the substrate, the anti-reflective structure comprising an anti-reflective enhancement layer, the anti-reflective enhancement layer comprising a porous metal-based organic hybrid layer.

[0106] As an example of this embodiment, the anti-reflective enhancement layer can be a porous metal-based organic hybrid layer.

[0107] As another example of this embodiment, the anti-reflective enhancement layer comprises at least one porous metal-based organic hybrid layer and at least one metal oxide layer, the material of the metal oxide layer comprises a metal oxide, and the porous metal-based organic hybrid layer and the metal oxide layer are alternately stacked. It can be understood that each porous metal-based organic hybrid layer can have a porous structure, and each metal oxide layer can be attached to the pore wall surface of the immediately adjacent porous metal-based organic hybrid layer.

[0108] Figure 1 is a structural schematic diagram of an anti-reflective device according to an embodiment of the present disclosure. Referring to Figure 1, the anti-reflective device comprises a substrate 100 and an anti-reflective structure stacked on the substrate 100, the anti-reflective structure comprising an anti-reflective base layer 120 and an anti-reflective enhancement layer 110 stacked on the anti-reflective base layer 120, the anti-reflective enhancement layer 110 comprising a porous metal-based organic hybrid layer.

[0109] In the embodiment shown in FIG. 1, the antireflection base layer 120 includes a high-refractive-index film 121 and a low-refractive-index film 122. The high-refractive-index film 121 has a higher refractive index than the low-refractive-index film 122.

[0110] As an example of this embodiment, the substrate 100 can be a workpiece carrying the antireflection structure. The workpiece can be, but is not limited to, an optical lens. The material of the optical lens can be organic glass or inorganic glass.

[0111] In some examples, the organic glass is resin glass and the inorganic glass is K9 glass.

[0112] Referring to FIG. 1, in this embodiment, in the antireflection base layer 120, the film at the bottom layer is the high-refractive-index film 121 and the film at the top layer is the low-refractive-index film 122.

[0113] As an example of this embodiment, the high-refractive-index film 121 has a refractive index ≥ 1.5. Further, the high-refractive-index film 121 has a refractive index of 1.5-2.3.

[0114] As an example of this embodiment, the material of the high-refractive-index film 121 includes one or more of titanium oxide (TiO2), aluminum oxide (Al2O3), tantalum oxide (Ta2O3), and zirconium oxide (ZrO2). The refractive index of titanium oxide is about 2.31, the refractive index of aluminum oxide is about 1.62, the refractive index of tantalum oxide is about 2.11, and the refractive index of zirconium oxide is about 2.15. It can be understood that the refractive index of the high-refractive-index film 121 is related to its material, and the material of the high-refractive-index film 121 can be selected according to the required refractive index.

[0115] As an example of this embodiment, the thickness of the high-refractive-index film 121 is 3-30 nm. In some examples, the thickness of the high-refractive-index film 121 can be 3 nm, 5 nm, 6 nm, 7 nm, 8 nm, 10 nm, 12 nm, 15 nm, 17 nm, 20 nm, 25 nm, 30 nm, or the thickness of the high-refractive-index film 121 can also be between any two of the above thicknesses.

[0116] As an example of this embodiment, the low-refractive-index film 122 has a refractive index ≤ 1.5. Further, the low-refractive-index film 122 has a refractive index of 1.35-1.5.

[0117] As an example of this embodiment, the material of the low-refractive-index film 122 includes one or more of silicon oxide (SiO2) and magnesium fluoride (MgF2). The refractive index of silicon oxide is about 1.45 and the refractive index of magnesium fluoride is about 1.38. It can be understood that the refractive index of the low-refractive-index film 122 is related to its material, and the material of the low-refractive-index film 122 can be selected according to the required refractive index.

[0118] As an example of this embodiment, the thickness of the low-refractive-index film 122 is 40 nm to 120 nm.

[0119] In some examples, the thickness of the low-refractive-index film 122 can be 40 nm, 50 nm, 60 nm, 70 nm, 80 nm, 90 nm, 100 nm, 110 nm, 120 nm, or the thickness of the low-refractive-index film 122 can also be between any two thicknesses mentioned above.

[0120] Referring to FIG. 1, as an example of this embodiment, the antireflection enhancement layer 110 is a porous metal-based organic hybrid layer.

[0121] It can be understood that the refractive index of the porous metal-based organic hybrid layer can gradually change along the thickness direction, but the porous metal-based organic hybrid layer as a whole has an equivalent refractive index. As an example of this embodiment, the equivalent refractive index of the antireflection enhancement layer 110 is 1.2 to 1.5, i.e., the equivalent refractive index of the porous metal-based organic hybrid layer of this embodiment is 1.2 to 1.5.

[0122] Further, in this embodiment, the equivalent refractive index of the porous metal-based organic hybrid layer is 1.23 to 1.3. The porous metal-based organic hybrid layer with an equivalent refractive index in this range can achieve a significantly better effect of enhancing antireflection, which is conducive to obtaining an antireflection structure with a significantly lower reflectivity.

[0123] In some examples, the equivalent refractive index of the porous metal-based organic hybrid layer can be 1.23, 1.24, 1.25, 1.26, 1.27, 1.28, 1.29, 1.3, or the equivalent refractive index of the porous metal-based organic hybrid layer can also be between any two refractive indices mentioned above.

[0124] Overall, the equivalent refractive index of the porous metal-based organic hybrid layer is related to factors such as the thickness of the film, the pore size of the pores, and the porosity.

[0125] As an example of this embodiment, the thickness of the porous metal-based organic hybrid layer is 10 nm to 200 nm.

[0126] In some examples, the thickness of the porous metal-based organic hybrid layer can be 10 nm, 20 nm, 30 nm, 40 nm, 50 nm, 60 nm, 70 nm, 80 nm, 100 nm, 120 nm, 150 nm, 200 nm, or the thickness of the porous metal-based organic hybrid layer can also be between any two thicknesses mentioned above.

[0127] As an example of this embodiment, the pore size of the pores in the porous metal-based organic hybrid layer is 1 nm to 30 nm.

[0128] In some examples, the pore size of the pores in the porous metal-organic hybrid layer is about 1 nm, 2 nm, 3 nm, 5 nm, 7 nm, 10 nm, 12 nm, 14 nm, 15 nm, 17 nm, 20 nm, 25 nm, 30 nm, or the pore size of the pores in the porous metal-organic hybrid layer can also be between any two of the above.

[0129] As an example of this embodiment, the porosity of the porous metal-organic hybrid layer is 10% to 70%.

[0130] In some examples, the porosity of the porous metal-organic hybrid layer is 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, or the porosity of the porous metal-organic hybrid layer can also be between any two of the above.

[0131] As an example of this embodiment, the material of the porous metal-organic hybrid layer includes one or more of an aluminum-based hydroquinone hybrid material, a zinc-based hydroquinone hybrid material, and a titanium-based hydroquinone hybrid material. 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 can be obtained by reacting a zinc compound with hydroquinone, and the zinc compound can include but is not limited to diethylzinc. The titanium-based hydroquinone hybrid material can be obtained by reacting a titanium compound with hydroquinone, and the titanium compound can include but is not limited to titanium tetrachloride.

[0132] As an example of this embodiment, the porous metal-organic hybrid layer is formed by molecular layer deposition. In the process of molecular layer deposition, the porous structure can be directly formed in the porous metal-organic hybrid layer. By controlling the temperature and the number of deposition cycles in the deposition process, the porous structure in the porous metal-organic hybrid layer can be correspondingly controlled.

[0133] As an example of this embodiment, the raw material for preparing the porous metal-organic hybrid layer includes a first metal precursor and an organic precursor. The first metal precursor is selected from one or more of trimethylaluminum, diethylzinc, and titanium tetrachloride, and the organic precursor is selected from hydroquinone.

[0134] It can be understood that the material of the porous metal-based organic hybrid layer is related to the raw material for preparing the same. For example, if the material of the porous metal-based organic hybrid layer comprises an aluminum-based hydroquinone hybrid material, the first metal precursor can be trimethylaluminum, and the organic precursor can be hydroquinone. If the material of the porous metal-based organic hybrid layer comprises a zinc-based hydroquinone hybrid material, the first metal precursor can be zinc ethylene, and the organic precursor can be hydroquinone. If the material of the porous metal-based organic hybrid layer comprises a titanium-based hydroquinone hybrid material, the first metal precursor can be titanium tetrachloride, and the organic precursor can be hydroquinone.

[0135] As an example of this embodiment, the average reflectivity of the antireflection structure for light in the wavelength range of 400 nm to 800 nm is less than or equal to 0.2%.

[0136] FIG. 2 is a schematic structural diagram of an antireflection device according to another embodiment of the present disclosure. Referring to FIG. 2, the antireflection device comprises a substrate 200 and an antireflection structure stacked on the substrate 200, the antireflection structure comprising an antireflection base layer 220 and an antireflection enhancement layer 210 stacked on the antireflection base layer 220, the antireflection enhancement layer 210 comprising a porous metal-based organic hybrid layer. In the embodiment shown in FIG. 2, the antireflection base layer 220 comprises two layers of high-refractive-index films 221 and two layers of low-refractive-index films 222. The refractive index of the high-refractive-index film 221 is higher than that of the low-refractive-index film 222.

[0137] In this embodiment, the refractive index and thickness of the two layers of high-refractive-index films 221 can be different, and the refractive index and thickness of the two layers of low-refractive-index films 222 can also be different, which mainly depends on the required structural design of the antireflection base layer 220.

[0138] As an example of this embodiment, the substrate 200 can be a workpiece carrying the antireflection structure. The workpiece can be, but is not limited to, an optical lens. The material of the optical lens can be organic glass or inorganic glass.

[0139] In some examples, the organic glass is resin glass, and the inorganic glass is K9 glass.

[0140] Referring to FIG. 2, in this embodiment, in the antireflection base layer 220, the film at the bottom layer is the high-refractive-index film 221, and the film at the top layer is the low-refractive-index film 222.

[0141] As an example of this embodiment, the refractive index of the high-refractive-index film 221 is greater than or equal to 1.5. Further, the refractive index of the high-refractive-index film 221 is 1.5 to 2.3.

[0142] As an example of this embodiment, the material of the high-refractive-index film 221 comprises one or more of titanium oxide, aluminum oxide, tantalum oxide, and zirconium oxide.

[0143] As an example of this embodiment, the high refractive index film 221 has a thickness of 3 nm to 30 nm.

[0144] As an example of this embodiment, the low refractive index film 222 has a refractive index of ≤1.5. Further, the low refractive index film 222 has a refractive index of 1.35 to 1.5.

[0145] 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.

[0146] As an example of this embodiment, the low refractive index film 222 has a thickness of 40 nm to 120 nm.

[0147] As an example of this embodiment, the antireflection enhancement layer 210 includes at least one porous metal-based organic hybrid layer and at least one metal oxide layer, and the porous metal-based organic hybrid layer and the metal oxide layer are alternately stacked. The introduction of the metal oxide layer can realize the regulation of the pore structure in the antireflection enhancement layer 210, thereby enriching the performance of the antireflection enhancement layer 210.

[0148] Further, each porous metal-based organic hybrid layer can have a porous structure, and each metal oxide layer can be attached to the pore wall surface in the immediately adjacent porous metal-based organic hybrid layer.

[0149] As an example of this embodiment, the equivalent refractive index of the antireflection enhancement layer 210 is 1.2 to 1.5, that is, the equivalent refractive index of the stack structure composed of the porous metal-based organic hybrid layer and the metal oxide layer of this embodiment is 1.2 to 1.5.

[0150] Further, in this embodiment, the equivalent refractive index of the antireflection enhancement layer 210 is 1.23 to 1.3. The antireflection enhancement layer 210 with the equivalent refractive index in this range can play a significantly better effect of enhancing antireflection, which is conducive to obtaining an antireflection structure with a significantly lower reflectivity.

[0151] In some examples, the equivalent refractive index of the antireflection enhancement layer 210 can be 1.23, 1.24, 1.25, 1.26, 1.27, 1.28, 1.29, 1.3, or the equivalent refractive index of the antireflection enhancement layer 210 can also be between any two refractive indices described above.

[0152] Overall, the equivalent refractive index of the antireflection enhancement layer 210 is related to factors such as the thickness of the film, the pore size of the pores, and the porosity. In addition, the ratio of the number of depositions between the porous metal-based organic hybrid layer and the metal oxide layer during the deposition process also has a significant impact on the equivalent refractive index of the pore structure.

[0153] As an example of this embodiment, the thickness of the antireflection enhancement layer 210 is 10 nm to 200 nm.

[0154] In some examples, the thickness of the antireflection enhancement layer 210 can be 10 nm, 20 nm, 30 nm, 40 nm, 50 nm, 60 nm, 70 nm, 80 nm, 100 nm, 120 nm, 150 nm, 200 nm, or the thickness of the antireflection enhancement layer 210 can also be between any two thicknesses described above.

[0155] As an example of this embodiment, the pore size of the pores in the antireflection enhancement layer 210 is 1 nm to 30 nm.

[0156] In some examples, the pore size of the pores in the antireflection enhancement layer 210 is about 1 nm, 2 nm, 3 nm, 5 nm, 7 nm, 10 nm, 12 nm, 14 nm, 15 nm, 17 nm, 20 nm, 25 nm, 30 nm, or the pore size of the pores in the antireflection enhancement layer 210 can also be between any two pore sizes described above.

[0157] As an example of this embodiment, the porosity of the antireflection enhancement layer 210 is 10% to 70%.

[0158] In some examples, the porosity of the antireflection enhancement layer 210 is 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, or the porosity of the antireflection enhancement layer 210 can also be between any two porosities described above.

[0159] As an example of this embodiment, the material of the porous metal-based organic hybrid layer includes one or more of an aluminum-based hydroquinone hybrid material, a zinc-based hydroquinone hybrid material, and a titanium-based hydroquinone hybrid material.

[0160] As an example of this embodiment, the porous metal-based organic hybrid layer is prepared by a molecular layer deposition method.

[0161] As an example of this embodiment, the raw material for preparing the porous metal-based organic hybrid layer includes a first metal precursor and an organic precursor. The first metal precursor is selected from one or more of trimethylaluminum, zinc bisethylenate, and titanium tetrachloride, and the organic precursor is selected from hydroquinone.

[0162] As an example of this embodiment, the material of the metal oxide layer includes one or more of aluminum oxide, zinc oxide, and titanium oxide.

[0163] As an example of this embodiment, the metal oxide layer is prepared by an atomic layer deposition method.

[0164] As an example of this embodiment, the metal element in the metal oxide layer is the same as the metal element in the porous metal-based organic hybrid layer. This facilitates the metal oxide layer to bind more closely with the porous metal-based organic hybrid layer, enhancing the stability of the stacked structure.

[0165] It can be understood that the process of molecular layer deposition and the process of atomic layer deposition both include multiple deposition cycles.

[0166] As an example of this embodiment, the ratio between the number of deposition cycles of the porous metal-based organic hybrid layer and the number of deposition cycles of the metal oxide layer can be 1:(1-5).

[0167] In some examples, the ratio between the number of deposition cycles of the porous metal-based organic hybrid layer and the number of deposition cycles of the metal oxide layer can be 1:1, 1:2, 1:3, 1:4, 1:5, or the ratio between the number of deposition cycles of the two can be between any two of the above ratios. As the ratio increases, the pore size and porosity in the formed stacked structure will decrease, thereby obtaining a higher equivalent refractive index of the antireflection enhancement layer 210.

[0168] As an example of this embodiment, the average reflectivity of the antireflection structure for light in the 400-800 nm wavelength band is below 0.2%.

[0169] In a second aspect, the disclosure provides a method for manufacturing an optical device, the method comprising the steps of:

[0170] manufacturing a porous film, the manufacturing method of the porous film comprising a molecular deposition method, the porous film comprising a porous metal oxide layer or a porous metal-based organic hybrid layer, the porous film being used to reduce reflected light on the workpiece body;

[0171] arranging the porous film on the workpiece body.

[0172] As an example of this embodiment, the porous film comprises a porous metal oxide layer, and the manufacturing method of the porous film comprises the steps of: manufacturing at least one layer of a first precursor monolayer and at least one layer of a second precursor monolayer on a substrate, the material of the first precursor monolayer and the material of the second precursor monolayer being capable of forming a hydrolysable metal-organic composite layer after reaction. The metal-organic composite layer is placed in a water-containing environment to perform a hydrolysis reaction, so that the metal-organic composite layer is converted to form a porous metal oxide layer.

[0173] In the actual preparation process, the single molecular layers can be attached to the base material to form the first precursor monolayer and the second precursor monolayer. It can be understood that the first precursor monolayer and the second precursor monolayer can be combined by a chemical reaction to form a metal-organic composite layer, and the material of the metal-organic composite layer can be hydrolyzed to form an oxide of the metal. The hydrolysis reaction of the metal-organic composite layer with water causes the material of the metal-organic composite layer to gradually decompose and causes the structure of the metal-organic composite layer to change, thereby generating a pore structure. It is found in the research of the present disclosure that the pore structure and the pore size are closely related to the conditions (such as time and temperature) of the hydrolysis reaction. By controlling the conditions of the hydrolysis reaction, the surface hydrolysis rate of the metal-organic composite layer can be controlled, thereby achieving accurate control of the pore structure and the pore size in the porous metal oxide layer.

[0174] In the preparation method of the porous membrane of the present disclosure, the first precursor monolayer and the second precursor monolayer are combined to form a metal-organic composite layer. Since the first precursor monolayer and the second precursor monolayer are prepared and reacted in the form of monolayers, the interference of random factors can be effectively avoided and the process is easy to reproduce, so that the structure of the metal-organic composite layer is highly controllable and has high reproducibility. Then, the metal-organic composite layer is subjected to a hydrolysis reaction with water, so that the metal-organic composite layer is converted into a porous metal oxide layer with a porous structure. The pore structure in the porous metal oxide layer is related to the structure of the metal-organic composite layer and the hydrolysis conditions, and by controlling the hydrolysis conditions and the structure of the metal-organic composite layer, the pore structure and the size thereof can be accurately controlled. Therefore, by combining the formation of the metal-organic composite layer and the hydrolysis reaction, the controllability of the pore structure can be effectively improved.

[0175] As some examples of this embodiment, the preparation method of the porous membrane further includes the following steps:

[0176] A shape-retaining layer for reinforcing the porous metal oxide layer is prepared on the porous metal oxide layer.

[0177] The further formed shape-retaining layer can also improve the air stability and the friction resistance of the porous metal oxide layer without substantially changing the pore structure, so that the prepared porous membrane also has high stability.

[0178] Compared with the traditional template method or sol-gel method, the preparation method of the porous film can realize rapid, efficient and large-area preparation of the porous film by depositing molecular layers. Moreover, the preparation process is more simplified and the preparation efficiency is higher. The preparation method of the porous film can be prepared on various different substrates, and the selective deposition technology can also realize the regional selective generation of the porous film, meeting different application requirements. Further, it has been verified through experiments that the porous film prepared by the preparation method of the porous film has excellent antireflection effect. Understandably, the porous film with excellent antireflection effect has excellent transmittance effect.

[0179] FIG. 3 is a schematic diagram of the steps of the preparation method of the porous film of one embodiment of the present disclosure when the porous film includes a porous metal oxide layer. Referring to FIG. 3, the preparation method of the porous film includes steps S1-S3, which are as follows.

[0180] Step S1, preparing at least one layer of a first precursor monolayer and at least one layer of a second precursor monolayer on a substrate.

[0181] As some examples of this embodiment, the substrate can be a workpiece to be prepared into a porous film. The workpiece can be, but is not limited to, an optical lens. The material of the optical lens can be organic glass or inorganic glass. As an example, the organic glass is resin glass and the inorganic glass is K9 glass.

[0182] In this embodiment, the material of the first precursor monolayer and the material of the second precursor monolayer react to form a metal-organic composite layer that can be hydrolyzed. The metal-organic composite layer contains a metal-organic composite material, which refers to a material formed by the combination of metal atoms and carbon chains of organic matter. When hydrolyzed, the metal atoms can combine with the hydroxyl groups in water to form metal-hydroxyl compounds and ultimately form metal oxides.

[0183] As some examples of this embodiment, the metal-organic composite layer includes an aluminum-based organic-inorganic hybrid material.

[0184] It can be understood that the materials of the first precursor monolayer and the second precursor monolayer can be selected according to the required metal-organic composite layer. As some examples of this embodiment, the first precursor monolayer includes a metal-organic compound, and the second precursor monolayer includes an alcohol organic matter and / or its derivative.

[0185] As some examples of this embodiment, in the first precursor monolayer, the metal organic compound can be an alkyl metal compound. In this example, the metal atom in the alkyl metal compound can be selected from one or more of aluminum, gallium, indium, tin, lead, zinc, titanium, and cobalt. In this example, the alkyl group can have one or more depending on the coordination number of the metal atom in the alkyl metal compound. The alkyl group can be selected from alkyl groups having a carbon atom number of 1-20, for example, the alkyl group can be methyl, ethyl, propyl, butyl, and the like.

[0186] Further, the metal organic compound in the first precursor monolayer is trimethylaluminum. It can be understood that in other examples, the metal organic compound can also be, but is not limited to, triethylaluminum, tetramethyltin, dimethylzinc, and the like.

[0187] Further, the alcohol organic compound in the second precursor monolayer can be selected from one or more of ethylene glycol, glycerol, and ethanolamine.

[0188] In other examples, the alcohol organic compound can also be selected from one or more of propylene glycol, butanediol, and pentanediol. The derivative of the alcohol organic compound refers to the alcohol organic compound in which at least one hydrogen atom is replaced.

[0189] For example, with trimethylaluminum and a dihydric alcohol, the trimethylaluminum and the dihydric alcohol can react to form an alkoxyaluminum compound, which is the material of the metal organic composite layer.

[0190] As some examples of this embodiment, the first precursor monolayer and the second precursor monolayer each have multiple layers. It can be understood that the provision of the multiple layers of the first precursor monolayer and the multiple layers of the second precursor monolayer can form a thicker metal organic composite layer. Moreover, by controlling the number of layers of the first precursor monolayer and the second precursor monolayer, the thickness of the formed metal organic composite layer can be controlled. This is also conducive to precise control of the overall structure of the final porous metal oxide layer.

[0191] As some examples of this embodiment, the step of preparing the first precursor monolayer and the second precursor monolayer on the substrate includes: placing the substrate in a deposition chamber. The material of the first precursor monolayer is introduced into the deposition chamber and adhered to the substrate to form the first precursor monolayer. The material of the second precursor monolayer is introduced into the deposition chamber and adhered to the substrate to form the second precursor monolayer. In this example, the step of forming the first precursor monolayer and the step of forming the second precursor monolayer are repeated as one deposition cycle, and multiple deposition cycles are performed.

[0192] For example, a first precursor monolayer is formed on the substrate, and the first precursor monolayer is attached to the substrate. Then, a second precursor monolayer is formed, and the second precursor monolayer is attached to and reacts with the first precursor monolayer. Then, the first precursor monolayer and the second precursor monolayer are alternately deposited until a predetermined number of layers is reached. The first precursor monolayers deposited later are attached to the second precursor monolayers deposited earlier, and the second precursor monolayers deposited later are attached to the first precursor monolayers deposited earlier. The plurality of first precursor monolayers and the plurality of second precursor monolayers combine to form a metal-organic composite layer.

[0193] As some examples of this embodiment, a step of purging the deposition chamber can be included after each formation of the first precursor monolayer and the second precursor monolayer. The step of purging the deposition chamber includes introducing a protective gas into the deposition chamber to remove unreacted materials and by-products generated by the reaction, and to ensure the purity of the surface to ensure the continuous deposition.

[0194] It can be understood that, in this embodiment, the process of forming the first precursor monolayer and the second precursor monolayer on the substrate can be performed using a molecular layer deposition (MLD) device.

[0195] As some examples of this embodiment, the metal-organic composite layer formed has a thickness of 5 nm to 60 nm.

[0196] In this example, the metal-organic composite layer has a thickness of 5 nm, 10 nm, 15 nm, 20 nm, 25 nm, 30 nm, 35 nm, 40 nm, 45 nm, 50 nm, 55 nm, or 60 nm. Alternatively, the metal-organic composite layer can have a thickness between any two of the above-mentioned thicknesses. The metal-organic composite layer having the above-mentioned thickness is conducive to forming a porous metal oxide layer having a relatively stable pore structure and good light transmission performance in a subsequent hydrolysis process.

[0197] It can be understood that the thickness of the metal-organic composite layer can be controlled by controlling the number of deposition cycles.

[0198] As some examples of this embodiment, the number of deposition cycles can be 15 to 100. That is, 15 to 100 layers of the first precursor monolayer and 15 to 100 layers of the second precursor monolayer are alternately deposited. For example, the number of deposition cycles can be 15, 20, 25, 30, 40, 50, 60, 70, 80, 90, or 100, or the number of deposition cycles can be between any two of the above-mentioned numbers.

[0199] As some examples of this embodiment, the temperature of the deposition chamber during the formation of the first precursor monolayer and the second precursor monolayer is 50-200°C. Controlling the temperature of the deposition chamber within this range helps to make the first precursor monolayer adhere more fully and uniformly, and makes the process of the first precursor monolayer combining with the second precursor monolayer to form the metal-organic composite layer more controllable, thereby improving the controllability of the pore structure in the porous metal oxide layer formed subsequently.

[0200] In this preparation method, the first precursor monolayer and the second precursor monolayer can be deposited at a lower temperature, and thus is particularly suitable for preparation on some substrates with poor high-temperature resistance. For substrates with poor high-temperature resistance, the temperature of the deposition chamber during the formation of the first precursor monolayer and the second precursor monolayer can be 50-100°C. For example, the temperature of the deposition chamber can be 50°C, 60°C, 70°C, 80°C, 90°C, or 100°C. Alternatively, the temperature of the deposition chamber can also be between any two of the above temperatures.

[0201] In step S2, the metal-organic composite layer is placed in an aqueous environment to perform a hydrolysis reaction, so that the metal-organic composite layer is converted to form a porous metal oxide layer.

[0202] In this embodiment, the material of the porous metal oxide layer includes a metal oxide, and the metal element in the metal oxide is the same as the metal element in the metal-organic composite layer.

[0203] As some examples of this embodiment, the metal-organic composite layer can be placed in water to perform a hydrolysis reaction. Alternatively, in other examples, the metal-organic composite layer can also be placed in a humid gas environment containing water vapor to perform a hydrolysis reaction.

[0204] For example, in the hydrolysis reaction of an aluminum alkoxide compound (Al-O-CH2-CH2-O-Al), the aluminum alkoxide compound reacts with water to form an aluminum hydroxide compound (Al-OH), and the chemical reaction formula is as follows: Al-O-CH2-CH2-O-Al + H2O→ Al-OH + HO-CH2-CH2-O-Al. The aluminum hydroxide compound is further dehydrated to form aluminum oxide. In addition, the hydroxyl group in the aluminum hydroxide compound can also produce an alcoholate ion RO - (R represents a group connected to the hydroxyl group) during hydrolysis, and the chemical reaction formula is as follows: ROH + H2O→ RO - + H3O + The alcoholate ion can further react with water in the presence of carbon dioxide to produce a carboxylic acid (RCOOH), and the chemical reaction formula is as follows: RO - + CO + H2O→ RCOOH + OH -Therefore, the alcohol aluminum polymer can gradually transform into the porous aluminum oxide material containing hydroxyl and carboxyl functional groups on the surface through the hydrolysis reaction.

[0205] As some examples of this embodiment, the temperature of the hydrolysis reaction can be controlled to be 10-80℃ during the hydrolysis reaction. Controlling the temperature of the hydrolysis reaction can obtain a more optimized hydrolysis reaction rate, which is beneficial to more accurate control of the obtained pore structure. When the temperature of the hydrolysis reaction is too low, the hydrolysis reaction rate is too slow, which is not conducive to the formation of the porous structure. When the temperature of the hydrolysis reaction is too high, the hydrolysis reaction rate is too fast, which is not conducive to more accurate control of the porous structure.

[0206] In this example, the temperature of the hydrolysis reaction can be controlled to be 10℃, 15℃, 20℃, 25℃, 30℃, 35℃, 40℃, 50℃, 60℃, 70℃, 80℃, or the temperature of the hydrolysis reaction can also be controlled between any two of the above temperatures.

[0207] As some examples of this embodiment, the time of the hydrolysis reaction can be controlled to be 5-120min. Controlling the time of the hydrolysis reaction is conducive to controlling the progress of the hydrolysis reaction, which can realize the regulation of the pore size, shape and arrangement, etc., so as to prepare the porous metal oxide layer with controllable pore structure. And the time of the hydrolysis reaction is also conducive to obtaining the porous metal oxide layer with significantly higher transmittance.

[0208] In this example, the time of the hydrolysis reaction can be controlled to be 5min, 10min, 15min, 20min, 25min, 30min, 35min, 40min, 45min, 50min, 60min, 70min, 80min, 90min, 100min, 110min, 120min. Or, the time of the hydrolysis reaction can also be controlled between any two of the above times.

[0209] It can be understood that when the temperature of the hydrolysis reaction is higher, the hydrolysis reaction rate is faster, and the time of the hydrolysis reaction can be controlled to be shorter, that is, the required pore structure can be formed. When the temperature of the hydrolysis reaction is lower, the hydrolysis reaction rate is slower, and the time of the hydrolysis reaction can be controlled to be longer to form the required pore structure. In addition, the time of the hydrolysis reaction can also be controlled according to the thickness of the metal organic composite layer. For example, for a thicker metal organic composite layer, a longer hydrolysis reaction time can be used to ensure that the metal organic composite layer can be more fully hydrolyzed into a porous metal oxide layer.

[0210] As some examples of this embodiment, after the hydrolysis reaction, the step of drying the formed porous metal oxide layer is further included. The drying treatment is used to remove the residual moisture in the porous metal oxide layer.

[0211] In this example, the drying process is performed by blowing a protective gas on the porous metal oxide layer.

[0212] In this embodiment, the porous metal oxide layer generated by the hydrolysis reaction also has a poor stability problem, which causes the porous structure of the layer to be easily damaged and easily fall off from the surface of the substrate. As some examples of this embodiment, a step of performing a shaping process on the porous metal oxide layer can be further included after the porous metal oxide layer is formed.

[0213] In this example, the step of performing a shaping process on the porous metal oxide layer includes placing the porous metal oxide layer in a protective gas environment and heating the porous metal oxide layer. By heating the porous metal oxide layer, the porous structure therein can be shaped and the bonding strength between the porous metal oxide layer and the substrate can be enhanced.

[0214] In this example, the heating temperature is 50°C to 80°C when the porous metal oxide layer is heated. For example, the heating temperature can be 50°C, 55°C, 60°C, 65°C, 70°C, 75°C, 80°C, or the heating temperature can also be in a range between any two of the above temperatures.

[0215] As some examples of this embodiment, the heating time is 5 min to 10 min when the porous metal oxide layer is heated. For example, the heating time can be 5 min, 6 min, 7 min, 8 min, 9 min, 10 min, or the heating time can also be in a range between any two of the above times.

[0216] Step S3, a shaping layer for reinforcing the porous metal oxide layer is prepared on the porous metal oxide layer.

[0217] In this embodiment, the shaping layer covers the surface of the porous metal oxide layer. It can be understood that the surface of the porous metal oxide layer is porous, and the shaping layer can be attached to the pore walls therein. The shaping layer can reinforce the porous structure of the porous metal oxide layer, so that the porous metal oxide layer can maintain the porous structure when it is subjected to external forces such as friction. And the shaping layer also makes the porous metal oxide layer be able to stably adhere to the substrate.

[0218] As some examples of this embodiment, the material of the shaping layer is selected from oxides. The oxides have a similar material structure to the porous metal oxide layer, which makes the shaping layer and the porous metal oxide layer be able to be more closely combined.

[0219] In this example, the material of the shaping layer can be selected from one or more of titanium dioxide, aluminum oxide, and silicon dioxide.

[0220] In this example, the material of the shaping layer is the same as the material of the porous metal oxide layer.

[0221] As some examples of this embodiment, the thickness of the shape-preserving layer is ≤ 10 nm. With a thickness of the shape-preserving layer below 10 nm, it is possible to avoid as much as possible that the shape-preserving layer fills up the pore structure and maintains the original pore structure of the porous metal oxide layer. Optionally, the thickness of the shape-preserving layer can be 1 nm to 3 nm. This is advantageous for obtaining a good shape-preserving performance while not substantially changing the pore structure.

[0222] In this example, the thickness of the shape-preserving layer can be 1 nm, 1.5 nm, 2 nm, 2.5 nm, 3 nm, or the thickness of the shape-preserving layer can also be between any two of the above thicknesses.

[0223] As some examples of this embodiment, the way of preparing the shape-preserving layer on the porous metal oxide layer is selected from one or more of chemical vapor deposition (CVD), physical vapor deposition (PVD), atomic layer deposition (ALD), molecular layer deposition, and liquid phase epitaxy. More preferably, atomic layer deposition is used to prepare a shape-preserving layer with a thinner and more uniform thickness, which provides a better shape-preserving performance while reducing the impact on the light transmission performance as much as possible.

[0224] It can be understood that through steps S1 to S3, a porous film can be prepared.

[0225] As some examples of this embodiment, the porous film comprises a porous metal-based organic hybrid layer, and the method of preparing the porous film comprises the following steps:

[0226] The porous metal-based organic hybrid layer is deposited by molecular layer deposition.

[0227] As some examples of this embodiment, the material of the porous metal-based organic hybrid layer comprises one or more of an aluminum-based hydroquinone hybrid material, a zinc-based hydroquinone hybrid material, and a titanium-based hydroquinone hybrid material.

[0228] In this example, the step of depositing the porous metal-based organic hybrid layer comprises: introducing a first metal precursor into a deposition chamber and allowing it to adhere to the substrate to form a first monolayer, introducing an organic precursor into the deposition chamber and allowing it to adhere to the substrate to form a second monolayer. Wherein the step of forming the first monolayer and the step of forming the second monolayer as a whole are a first deposition cycle. It can be understood that each deposition cycle can form a layer of metal-based organic hybrid material, and multiple deposition cycles in succession form a continuous porous metal-based organic hybrid layer.

[0229] In this example, the first metal precursor is selected from one or more of trimethylaluminum, zinc bisethyl, and titanium tetrachloride, and the organic precursor is selected from hydroquinone.

[0230] As an example of this embodiment, the number of first deposition cycles is 40 to 500. It can be appreciated that the number of first deposition cycles is related to the thickness of the porous metal-based organic hybrid layer, the more the number of first deposition cycles, the thicker the thickness of the porous metal-based organic hybrid layer. Also, the number of first deposition cycles is also related to the pore structure in the porous metal-based organic hybrid layer. Generally, as the number of first deposition cycles increases, both the porosity and the pore size in the porous metal-based organic hybrid layer show a trend of first significantly increasing and then slightly decreasing.

[0231] In some examples, the number of first deposition cycles can be 40, 60, 80, 100, 120, 150, 200, 250, 300, 400, 500, or the number of first deposition cycles can also be between any two of the above numbers.

[0232] As an example of this embodiment, after each formation of the first monolayer and after each formation of the second monolayer, a step of purging the deposition chamber can be included. The step of purging the deposition chamber includes introducing a protective gas into the deposition chamber to remove unreacted materials and by-products generated by the reaction. This is beneficial to ensure the purity of the surface of the previously formed material to ensure the continuous deposition.

[0233] As an example of this embodiment, in the step of depositing the porous metal-based organic hybrid layer, the temperature of the deposition chamber is controlled to be 150-300°C. It has been verified by experiments that the temperature of the deposition chamber will affect the pore size and the porosity of the formed porous metal-based organic hybrid layer, and controlling the temperature of the deposition chamber to be 150-300°C is beneficial to obtain a porous metal-based organic hybrid layer with more suitable pore size and porosity.

[0234] In some examples, in the step of depositing the porous metal-based organic hybrid layer, the temperature of the deposition chamber can be controlled to be 150°C, 170°C, 200°C, 220°C, 250°C, 270°C, 300°C, or the temperature of the deposition chamber can also be controlled to be between any two of the above temperatures.

[0235] It can be appreciated that the porous metal-based organic hybrid layer constitutes an antireflection enhancement layer, and thus the preparation of the antireflection enhancement layer is completed through the above steps.

[0236] As a further example of this embodiment, the method for preparing the porous film further includes the following step: depositing a metal oxide layer, and the step of depositing the porous metal-based organic hybrid layer and the step of depositing the metal oxide layer are alternately performed.

[0237] In this example, the way of depositing the metal oxide layer can be atomic layer deposition. By using atomic layer deposition, it is not only beneficial to make the metal oxide layer uniformly adhere to the pore wall of the previously prepared porous metal-based organic hybrid layer, but also beneficial to improve the continuity of the preparation process between the porous metal-based organic hybrid layer and the metal oxide layer.

[0238] As an example of this embodiment, the step of depositing the porous metal-based organic hybrid layer and the step of depositing the metal oxide layer can be sequentially performed in the same deposition chamber.

[0239] As an example of this embodiment, the step of depositing the metal oxide layer includes: introducing a second metal precursor into the deposition chamber and making it adhere to the substrate to form a third monolayer. Introducing an oxidizing agent into the deposition chamber and making it adhere to the substrate to form a fourth monolayer. The steps of forming the third monolayer and forming the fourth monolayer as a whole are taken as one second deposition cycle, and the second deposition cycle is repeated for multiple times.

[0240] Wherein, at least one first deposition cycle is continuously performed to form a layer of porous metal-based organic hybrid layer, at least one second deposition cycle is continuously performed to form a layer of metal oxide layer, and at least one layer of porous metal-based organic hybrid layer and at least one layer of metal oxide layer are alternately formed. It can be understood that at least one layer of porous metal-based organic hybrid layer and at least one layer of metal oxide layer can be alternately formed. Each layer of porous metal-based organic hybrid layer can have a porous structure.

[0241] In this example, when each layer of porous metal-based organic hybrid layer is formed, only one first deposition cycle can be performed. Accordingly, after each first deposition cycle is performed to form each layer of porous metal-based organic hybrid layer, one or more second deposition cycles can be continuously performed to form a layer of metal oxide layer. It can be understood that in other examples, when each layer of porous metal-based organic hybrid layer is formed, multiple first deposition cycles can also be continuously performed.

[0242] In this example, the second metal precursor is selected from one or more of trimethylaluminum, ethylenediamine zinc, and titanium tetrachloride. In further examples, the first metal precursor and the second metal precursor are selected from the same material.

[0243] Wherein, the oxidizing agent can be selected from one or more of ozone and water.

[0244] As an example of this embodiment, in the step of depositing the metal oxide layer, the temperature of the deposition chamber is controlled to be 150°C to 300°C.

[0245] In some examples, the temperature of the deposition chamber can be controlled to be 150°C, 170°C, 200°C, 220°C, 250°C, 270°C, 300°C, or the temperature of the deposition chamber can be controlled to be between any two of the above temperatures during the step of depositing the metal oxide layer.

[0246] It can be appreciated that the metal oxide layer and the porous metal-based organic hybrid layer constitute the antireflection enhancement layer. Then, the antireflection enhancement layer can be prepared by the above steps, and at this time, the metal oxide layer is attached to the pore wall of the porous metal-based organic hybrid layer.

[0247] As an example of this embodiment, the ratio of the number of times of performing the first deposition cycle to the number of times of performing the second deposition cycle is 1: (1-5).

[0248] In some examples, the ratio of the number of times of performing the first deposition cycle to the number of times of performing the second deposition cycle can be 1:1, 1:2, 1:3, 1:4, 1:5, or the ratio of the number of times of the two deposition cycles can also be between any two of the above ratios.

[0249] As a further example of this embodiment, the ratio of the number of times of performing the first deposition cycle to the number of times of performing the second deposition cycle is 1: (1-5) each time the porous metal-based organic hybrid layer and the subsequent metal oxide layer are formed.

[0250] As an example of this embodiment, as an example of this embodiment, before preparing the antireflection enhancement layer, the following step is further included: preparing an antireflection base layer on the substrate. In one example, the method for preparing the porous film includes the following steps:

[0251] providing the substrate;

[0252] preparing an antireflection base layer on the substrate;

[0253] placing the substrate in a deposition chamber to prepare an antireflection enhancement layer on the substrate, wherein the step of preparing the antireflection enhancement layer includes: depositing to form the porous metal-based organic hybrid layer; or the step of preparing the antireflection enhancement layer includes: depositing to form the porous metal-based organic hybrid layer and depositing to form the metal oxide layer, and the step of depositing to form the porous metal-based organic hybrid layer and the step of depositing to form the metal oxide layer are performed alternately.

[0254] The method for preparing the porous film of one embodiment of the present disclosure includes steps S1-S3, which are as follows.

[0255] Step S1, providing a substrate.

[0256] As an example of this embodiment, the substrate can be a workpiece carrying the anti-reflective structure. The workpiece can be, but is not limited to, an optical lens. The material of the optical lens can be organic glass or inorganic glass.

[0257] In some examples, the organic glass is resin glass and the inorganic glass is K9 glass.

[0258] Step S2, preparing an anti-reflective base layer on the substrate.

[0259] As an example of this embodiment, the step of preparing the anti-reflective base layer on the substrate comprises:

[0260] alternately depositing a high-refractive-index film and a low-refractive-index film on the substrate, the refractive index of the high-refractive-index film being higher than that of the low-refractive-index film, and each of the high-refractive-index film and the low-refractive-index film having at least one layer.

[0261] As an example of this embodiment, the material of the high-refractive-index film comprises one or more of titanium oxide, aluminum oxide, tantalum oxide and zirconium oxide.

[0262] As an example of this embodiment, the material of the low-refractive-index film comprises one or more of silicon oxide and magnesium fluoride.

[0263] It can be understood that the materials and the number of layers of the high-refractive-index film and the low-refractive-index film can be set according to specific requirements.

[0264] As an example of this embodiment, the method of preparing the high-refractive-index film can be physical vapor deposition or atomic layer deposition.

[0265] As an example of this embodiment, the method of preparing the low-refractive-index film can be physical vapor deposition or atomic layer deposition.

[0266] Step S3, placing the substrate in a deposition chamber to prepare an anti-reflective enhancement layer on the substrate.

[0267] The step of preparing the anti-reflective enhancement layer comprises: depositing a porous metal-based organic hybrid layer.

[0268] As an example of this embodiment, the material of the porous metal-based organic hybrid layer comprises one or more of aluminum-based hydroquinone hybrid material, zinc-based hydroquinone hybrid material and titanium-based hydroquinone hybrid material.

[0269] As an example of this embodiment, the way of depositing the metal-based organic hybrid material is molecular layer deposition.

[0270] In this example, the step of depositing the porous metal-based organic hybrid layer comprises: introducing a first metal precursor into the deposition chamber and allowing it to adhere to the substrate to form a first monolayer, introducing an organic precursor into the deposition chamber and allowing it to adhere to the substrate to form a second monolayer. The step of forming the first monolayer and the step of forming the second monolayer are collectively regarded as a first deposition cycle. It can be understood that each deposition cycle can form a layer of metal-based organic hybrid material, and a plurality of deposition cycles performed in succession form a continuous porous metal-based organic hybrid layer.

[0271] In this example, the first metal precursor is selected from one or more of trimethylaluminum, diethylzinc, and titanium tetrachloride, and the organic precursor is selected from hydroquinone.

[0272] As an example of this embodiment, the number of first deposition cycles is 40 to 500. It can be understood that the number of first deposition cycles is related to the thickness of the porous metal-based organic hybrid layer, and the more the number of first deposition cycles, the thicker the porous metal-based organic hybrid layer. In addition, the number of first deposition cycles is also related to the pore structure in the porous metal-based organic hybrid layer. In general, as the number of first deposition cycles increases, both the porosity and the pore size in the porous metal-based organic hybrid layer show a trend of first increasing significantly and then slightly decreasing.

[0273] In some examples, the number of first deposition cycles can be 40, 60, 80, 100, 120, 150, 200, 250, 300, 400, 500, or the number of first deposition cycles can also be between any two of the above numbers.

[0274] As an example of this embodiment, after each formation of the first monolayer and after each formation of the second monolayer, a step of purging the deposition chamber can be included. The step of purging the deposition chamber comprises introducing a protective gas into the deposition chamber to remove unreacted materials and by-products generated by the reaction. This is beneficial to ensure the purity of the surface of the previously formed material to ensure the continuous deposition.

[0275] As an example of this embodiment, in the step of depositing the porous metal-based organic hybrid layer, the temperature of the deposition chamber is controlled to be 150°C to 300°C. It has been verified by experiments that the temperature of the deposition chamber affects the pore size and porosity of the formed porous metal-based organic hybrid layer, and controlling the temperature of the deposition chamber to be 150°C to 300°C is beneficial to obtain a porous metal-based organic hybrid layer with more suitable pore size and porosity.

[0276] In some examples, the temperature of the deposition chamber can be controlled to be 150°C, 170°C, 200°C, 220°C, 250°C, 270°C, 300°C, or alternatively, the temperature of the deposition chamber can be controlled to be between any two of the above temperatures during the step of depositing the porous metal-based organic hybrid layer.

[0277] It can be appreciated that if the antireflection enhancement layer is a porous metal-based organic hybrid layer, the preparation of the antireflection enhancement layer can be completed by the above steps.

[0278] As a further example of this embodiment, the step of preparing the antireflection enhancement layer further comprises depositing a metal oxide layer, and the step of depositing the porous metal-based organic hybrid layer and the step of depositing the metal oxide layer are performed alternately.

[0279] In this example, the metal oxide layer can be deposited by atomic layer deposition. By using atomic layer deposition, not only can the metal oxide layer be uniformly attached to the pore walls of the previously prepared porous metal-based organic hybrid layer, but also the continuity of the preparation process between the porous metal-based organic hybrid layer and the metal oxide layer can be improved.

[0280] As an example of this embodiment, the step of depositing the porous metal-based organic hybrid layer and the step of depositing the metal oxide layer can be performed in the same deposition chamber.

[0281] As an example of this embodiment, the step of depositing the metal oxide layer comprises: introducing a second metal precursor into the deposition chamber and allowing it to adhere to the substrate to form a third monolayer. Introducing an oxidizing agent into the deposition chamber and allowing it to adhere to the substrate to form a fourth monolayer. The steps of forming the third monolayer and forming the fourth monolayer are collectively regarded as one second deposition cycle, and the second deposition cycle is repeated multiple times.

[0282] In this example, at least one first deposition cycle is continuously performed to form a layer of porous metal-based organic hybrid layer, at least one second deposition cycle is continuously performed to form a layer of metal oxide layer, and at least one layer of porous metal-based organic hybrid layer and at least one layer of metal oxide layer are alternately formed. It can be appreciated that at least one layer of porous metal-based organic hybrid layer and at least one layer of metal oxide layer can be alternately formed. Each layer of porous metal-based organic hybrid layer can have a porous structure.

[0283] In this example, when each layer of porous metal-based organic hybrid layer is formed, only one first deposition cycle can be performed. Accordingly, after each first deposition cycle is performed to form each layer of porous metal-based organic hybrid layer, one or more second deposition cycles can be continuously performed to form a layer of metal oxide layer. It can be appreciated that in other examples, when each layer of porous metal-based organic hybrid layer is formed, multiple first deposition cycles can also be continuously performed.

[0284] In this example, the second metal precursor is selected from one or more of trimethylaluminum, diethyl zinc, and titanium tetrachloride. In further examples, the first metal precursor and the second metal precursor are selected from the same material.

[0285] In this example, the oxidizing agent is selected from one or more of ozone and water.

[0286] As an example of this embodiment, in the step of depositing the metal oxide layer, the temperature of the deposition chamber is controlled to be 150-300°C.

[0287] In some examples, in the step of depositing the metal oxide layer, the temperature of the deposition chamber can be controlled to be 150°C, 170°C, 200°C, 220°C, 250°C, 270°C, 300°C, or the temperature of the deposition chamber can also be controlled to be between any two of the above temperatures.

[0288] It can be understood that, if the antireflection enhancement layer comprises a porous metal-based organic hybrid layer and a metal oxide layer attached to the pore walls thereof, the preparation of the antireflection enhancement layer can be completed through the above steps.

[0289] As an example of this embodiment, the ratio of the number of times of performing the first deposition cycle to the number of times of performing the second deposition cycle is 1:(1-5).

[0290] In some examples, the ratio of the number of times of performing the first deposition cycle to the number of times of performing the second deposition cycle can be 1:1, 1:2, 1:3, 1:4, 1:5, or the ratio of the number of times of performing the two deposition cycles can also be between any two of the above ratios.

[0291] As a further example of this embodiment, in each time of forming the porous metal-based organic hybrid layer and the subsequent metal oxide layer, the ratio of the number of times of performing the first deposition cycle to the number of times of performing the second deposition cycle is 1:(1-5).

[0292] Further, the present disclosure also provides an application of the porous metal-based organic hybrid layer in an antireflection structure. The antireflection structure comprises an antireflection enhancement layer, and the antireflection enhancement layer comprises a porous metal-based organic hybrid layer, and the porous metal-based organic hybrid layer has a porous structure.

[0293] Further, the present disclosure also provides an application of the porous metal-based organic hybrid layer in an antireflection structure. The antireflection structure comprises an antireflection base layer and an antireflection enhancement layer which is stacked on the antireflection base layer, and the antireflection enhancement layer comprises a porous metal-based organic hybrid layer, and the porous metal-based organic hybrid layer has a porous structure.

[0294] In this embodiment, the porous metal-based organic hybrid layer is the porous metal-based organic hybrid layer described in any of the above embodiments.

[0295] As an example of this embodiment, the equivalent refractive index of the antireflection enhancement layer as a whole is 1.2-1.5.

[0296] As an example of this embodiment, the thickness of the antireflection enhancement layer is 10-200 nm.

[0297] As an example of this embodiment, the pore size of the pores in the antireflection enhancement layer is 1-30 nm.

[0298] As an example of this embodiment, the porosity of the antireflection enhancement layer is 10-70%.

[0299] As an example of this embodiment, the material of the porous metal-based organic hybrid layer includes one or more of an aluminum-based hydroquinone hybrid material, a zinc-based hydroquinone hybrid material, and a titanium-based hydroquinone hybrid material.

[0300] As an example of this embodiment, the porous metal-based organic hybrid layer is formed by a molecular layer deposition method.

[0301] The raw materials for preparing the porous metal-based organic hybrid layer include a first metal precursor and an organic precursor; wherein,

[0302] As an example of this embodiment, the first metal precursor is selected from one or more of trimethylaluminum, zinc bisethyl, and titanium tetrachloride, and the organic precursor is selected from hydroquinone.

[0303] In a third aspect, the present disclosure also provides an application of a porous film in an antireflection film of an optical device, the porous film including a porous metal oxide layer or a porous metal-based organic hybrid layer.

[0304] In this embodiment, the porous metal oxide layer is the porous metal oxide layer described in any of the above embodiments. The porous metal-based organic hybrid layer is the porous metal-based organic hybrid layer described in any of the above embodiments.

[0305] As an example of this embodiment, the method for preparing the porous film includes a molecular layer deposition method. The method for preparing the porous metal oxide layer includes a molecular layer deposition method. The method for preparing the porous metal-based organic hybrid layer includes a molecular layer deposition method. Understandably, the methods for preparing the porous metal oxide layer and the porous metal-based organic hybrid layer are the methods described in any of the above embodiments.

[0306] The present disclosure also provides the following embodiments to further illustrate some implementation manners of the above preparation method. Accordingly, the present disclosure also provides the following comparative examples to illustrate the advantages of the preparation method.

[0307] Example 1

[0308] K9 glass was used as the substrate, and the substrate was placed in a deposition chamber of a molecular layer deposition device.

[0309] The temperature in the deposition chamber was controlled at 120°C, trimethylaluminum was introduced into the deposition chamber to adhere to the substrate to form a first precursor monolayer, and then argon was introduced into the deposition chamber to perform a purging treatment to remove unadhered trimethylaluminum and other byproducts. Ethylene glycol was then introduced into the deposition chamber to adhere to the first precursor monolayer, and then argon was introduced into the deposition chamber to perform a purging treatment to remove unadhered ethylene glycol and other byproducts. The steps of introducing trimethylaluminum and ethylene glycol were repeated 50 times to form an aluminum alkoxide polymer as a metal-organic composite layer.

[0310] The substrate was immersed in pure water to perform a hydrolysis reaction, the water temperature was controlled at 50°C, and the hydrolysis time was 45 min to form a porous metal oxide layer. After the hydrolysis, the substrate was taken out and blown with a nitrogen gun for 2 min until there was no residual water stain on the surface.

[0311] The substrate was transferred to an oven at a temperature of 75°C for heating for 10 min to allow the pore structure to be shaped.

[0312] The substrate was transferred to a deposition chamber of an atomic layer deposition device, and an aluminum oxide material with a thickness of 2 nm was deposited as a shaping layer.

[0313] Example 2

[0314] Example 2 was basically the same as Example 1, except that when the metal-organic composite layer was prepared, the steps of introducing trimethylaluminum and ethylene glycol were repeated 75 times; and when the hydrolysis reaction was performed, the water temperature was controlled at 30°C, and the hydrolysis time was 60 min.

[0315] Example 3

[0316] Example 3 was basically the same as Example 1, except that when the metal-organic composite layer was prepared, the steps of introducing trimethylaluminum and ethylene glycol were repeated 40 times; and when the hydrolysis reaction was performed, the water temperature was controlled at 10°C, and the hydrolysis time was 100 min.

[0317] Example 4

[0318] Example 4 was basically the same as Example 1, except that polymethyl methacrylate was used as the substrate; when the metal-organic composite layer was prepared, the steps of introducing trimethylaluminum and ethylene glycol were repeated 80 times; and when the hydrolysis reaction was performed, the water temperature was controlled at 30°C, and the hydrolysis time was 60 min.

[0319] Example 5

[0320] Example 5 is substantially the same as Example 1, except that in preparing the metal-organic composite layer, glycerol is used instead of ethylene glycol, and the steps of introducing trimethylaluminum and glycerol are repeated 100 times; in performing the hydrolysis reaction, the water temperature is controlled at 50°C, and the hydrolysis time is 30 min; and in preparing the shape-preserving layer, a 2-nm-thick titanium dioxide material is deposited.

[0321] Example 6

[0322] Example 6 is substantially the same as Example 1, except that polycarbonate is used as the substrate; in preparing the metal-organic composite layer, ethanolamine is used instead of ethylene glycol, and the steps of introducing trimethylaluminum and ethanolamine are repeated 90 times; in performing the hydrolysis reaction, the water temperature is controlled at 80°C, and the hydrolysis time is 5 min; and in preparing the shape-preserving layer, a 2-nm-thick silicon dioxide material is deposited.

[0323] Example 7

[0324] Example 7 is substantially the same as Example 1, except that in preparing the shape-preserving layer, the substrate is transferred to a deposition chamber of a chemical vapor deposition apparatus, and a 2-nm-thick aluminum oxide material is deposited by chemical vapor deposition.

[0325] Example 8

[0326] Example 8 is substantially the same as Example 1, except that in preparing the shape-preserving layer, the substrate is transferred to a deposition chamber of a magnetron sputtering apparatus, and a 2-nm-thick aluminum oxide material is deposited by magnetron sputtering.

[0327] Example 9

[0328] Example 9 is substantially the same as Example 1, except that in preparing the shape-preserving layer, a 5-nm-thick aluminum oxide material is deposited.

[0329] Example 10

[0330] Example 10 is substantially the same as Example 1, except that in preparing the shape-preserving layer, a 0.5-nm-thick aluminum oxide material is deposited.

[0331] Example 11

[0332] Example 11 is substantially the same as Example 1, except that after the hydrolysis and before the preparation of the shape-preserving layer, the step of heating to set the pore structure is not performed.

[0333] Example 12

[0334] Example 12 is substantially the same as Example 1, except that the hydrolysis temperature is 100°C.

[0335] Example 13

[0336] Example 13 is substantially the same as Example 1, except that the hydrolysis time is 200 min.

[0337] Example 14

[0338] Example 14 is substantially the same as Example 1, except that after the heating to fix the pore structure, the step of preparing a structure-preserving layer is not performed.

[0339] Comparative Example 1

[0340] Comparative Example 1 is substantially the same as Example 1, except that after the preparation of the metal-organic composite layer, the substrate is directly transferred to a muffle furnace and heated to 500°C in an air atmosphere for calcination, and then a 2 nm-thick aluminum oxide material is deposited on the surface of the calcined material.

[0341] Test 1: Two samples from Example 1, before and after the fixing treatment, are respectively taken, and after standing in air for a certain period of time, the surface morphology of the samples is observed using a microscope. The results can be seen in FIG. 4. The left image in FIG. 4 is a surface morphology photograph of the sample before the fixing treatment after standing for 20 h, and the right image in FIG. 4 is a surface morphology photograph of the sample after the fixing treatment after standing for 100 h.

[0342] As can be seen from FIG. 4, when not subjected to the fixing treatment, the film layer on the surface of the substrate has local bubbling, cracking and peeling phenomena after standing for 20 h, while after the fixing treatment, even after standing for 100 h, the film layer on the surface of the substrate still does not show obvious abnormalities. This shows that the heating and baking method can effectively stabilize the pore structure of the porous metal oxide layer.

[0343] Test 2: The samples prepared in Example 1 and Example 14 are respectively taken, and after being wiped with steel wool, the surface morphology of the samples is observed using a microscope. The results can be seen in FIG. 5. The left image in FIG. 5 is a surface morphology photograph of the sample of Example 1 after being wiped, and the right image in FIG. 5 is a surface morphology photograph of the sample of Example 14 after being wiped.

[0344] As can be seen from FIG. 5, Comparative Example 1 does not have a structure-preserving layer, and the surface film layer of Comparative Example 1 has bubbling, cracking and peeling phenomena after being wiped. Compared with Example 14 which does not have a further prepared structure-preserving layer, Example 1 further prepares a structure-preserving layer on the basis of the porous metal oxide layer, and even after being wiped with steel wool, the surface film layer of Example 1 still does not have the problem of bubbling and peeling. This shows that the design of the structure-preserving layer structure can effectively ensure the structural stability of the porous metal oxide layer.

[0345] Test 3: The surface morphology of the samples of Example 1 to Example 3 was observed by scanning electron microscope, and the results can be seen in Figures 6 to 8. Among them, Figure 6 is the surface morphology of the sample of Example 1, Figure 7 is the surface morphology of the sample of Example 2, and Figure 8 is the surface morphology of the sample of Example 3.

[0346] Referring to Figures 6 to 8, different deposition cycles and different hydrolysis conditions were used in Example 1 to Example 3, respectively, and all of them can prepare a porous metal oxide layer with a specific pore structure. In Figure 6, the pore size distribution of the porous structure is between 35 nm and 105 nm. In Figure 7, the pore size distribution of the porous structure is between 62 nm and 90 nm. In Figure 8, the pore size distribution of the porous structure is between 75 nm and 95 nm. This shows that the pore structure is related to the thickness of the metal-organic composite layer and the hydrolysis condition, and also shows that the pore structure can be controlled by controlling the thickness of the metal-organic composite layer and the hydrolysis condition. Further, the hydrolysis temperature of Example 1 is 50°C, and because the hydrolysis temperature is relatively high, the hydrolysis rate is relatively fast, and the hydrolysis is relatively sufficient at 45 min. However, the size of the holes formed is more uneven, so the pore size distribution range is larger. The hydrolysis temperature of Example 2 is 30°C, and the hydrolysis is relatively sufficient at 60 min. The uniformity of the hole size is improved, and the pore size distribution range is reduced compared with Example 1. The hydrolysis temperature of Example 3 is 10°C, and the hydrolysis rate is slower, and it needs to be hydrolyzed for 100 min to be relatively sufficient. The uniformity of the hole size is higher than that of Example 2, and the pore size distribution range is further reduced compared with Example 2.

[0347] Test 4: The average transmittance of the porous film prepared in each example and comparative example between 450 nm and 675 nm was tested, and the surface morphology of each example and comparative example was observed after standing in air for 20 h, and then the surface morphology was observed after wiping the surface with steel wool. The results can be seen in Table 1. The transmittance curves of Example 1 to Example 3 with respect to the change of the incident light wavelength are shown in Figures 9 to 11, respectively.

[0348] Table 1

[0349] In the surface morphology after standing column of Table 1, “√” indicates that the film is flat and has no cracking abnormalities, and “○” indicates that there are a few cracks on the film surface. In the surface morphology after wiping column of Table 1, “√” indicates that the film has no blistering and peeling problem, “○” indicates that the film has a few blistering and peeling, and “×” indicates that the film has a large area of blistering and peeling.

[0350] Referring to FIGS. 9-11 and Table 1, the average transmittance of the porous films prepared in Examples 1-3 can be maintained at 99% or more in the wavelength range of 450 nm-675 nm. Referring to Table 1, the average transmittance of the porous films prepared in Examples 1-6 can all reach 99% or more, indicating that the preparation method of the present disclosure can prepare a porous film with a transmittance of 99% or more by hydrolyzing the metal-organic composite layer and then forming a shape-retaining layer.

[0351] Further, in Table 1, compared with Example 1, Example 14 does not form a shape-retaining layer, although Example 1 and Example 14 have similar average light transmittance, but Example 14 has a large area of bubbles and peeling on the surface, which causes the film of Example 14 to be not suitable for practical use. This also indicates that forming a relatively thin shape-retaining layer by atomic layer deposition does not significantly negatively affect the light transmittance of the porous metal oxide layer. Although Comparative Example 1 can form a porous metal oxide layer by direct calcination, the prepared film has a significantly lower light transmittance. This also indicates that the preparation method of the present disclosure can prepare a porous film with significantly higher light transmittance.

[0352] In addition, referring to Example 1 and Examples 12 and 13. Compared with Example 1, Example 12 uses a higher hydrolysis temperature, and Example 13 uses a longer hydrolysis time, both of which cause the transmittance of the porous film to decrease. This is mainly because the degree of hydrolysis is too deep, which negatively affects the light transmittance of the porous structure.

[0353] Referring to Example 1 and Example 11. Compared with Example 1, Example 11 does not perform baking before preparing the shape-retaining layer, which causes a few cracks on the surface after being placed, which not only negatively affects the structural stability of the porous film, but also causes the light transmittance of the porous film to decrease.

[0354] Referring to Example 1 and Examples 7 and 8. The transmittance of Examples 7 and 8 is significantly lower than that of Example 1, which is mainly because Example 7 uses chemical vapor deposition to prepare the shape-retaining layer, and Example 8 uses physical vapor deposition to prepare the shape-retaining layer, both of which have poor uniformity of the prepared shape-retaining layer, which affects the original light transmittance of the porous structure.

[0355] Referring to Example 1 and Examples 9 and 10. The shape-retaining layer of Example 9 is slightly thicker, which negatively affects the light transmittance of the porous structure, causing the light transmittance of the porous film to decrease. The shape-retaining layer of Example 10 is slightly thinner, although the light transmittance of the porous film of Example 10 is basically the same as that of Example 1, but the film is prone to a few bubbles and peeling after being wiped, and the structural stability is slightly poor.

[0356] Example 1.1

[0357] K9 glass was used as the substrate, which was placed in a deposition chamber of a molecular layer deposition apparatus.

[0358] Preparation of the porous metal-based organic hybrid layer: the temperature in the deposition chamber was controlled at 200°C, trimethylaluminum was used as the metal precursor, and hydroquinone was used as the organic precursor. A single deposition cycle was as follows: trimethylaluminum was introduced into the deposition chamber for 2 s, followed by argon purge for 30 s, then hydroquinone was introduced for 3 s, followed by argon purge for 60 s, and the flow rate of all the gases was controlled at 2000 seem. 250 deposition cycles were performed to form the porous metal-based organic hybrid layer as the antireflection enhancement layer.

[0359] Example 1.2

[0360] Example 1.2 differs from Example 1.1 only in that, in the step of preparing the porous metal-based organic hybrid layer, 50 deposition cycles were performed.

[0361] Example 1.3

[0362] Example 1.3 differs from Example 1.1 only in that, in the step of preparing the porous metal-based organic hybrid layer, 100 deposition cycles were performed.

[0363] Example 1.4

[0364] Example 1.4 differs from Example 1.1 only in that, in the step of preparing the porous metal-based organic hybrid layer, 500 deposition cycles were performed.

[0365] Example 1.5

[0366] Example 1.5 differs from Example 1.1 only in that, in the step of preparing the porous metal-based organic hybrid layer, the temperature in the deposition chamber was controlled at 150°C.

[0367] Example 1.6

[0368] Example 1.6 differs from Example 1.1 only in that, in the step of preparing the porous metal-based organic hybrid layer, the temperature in the deposition chamber was controlled at 250°C.

[0369] Example 1.7

[0370] Example 1.7 differs from Example 1.1 only in that, in the step of preparing the porous metal-based organic hybrid layer, the temperature in the deposition chamber was controlled at 300°C.

[0371] Example 1.8

[0372] Example 1.8 differs from Example 1.1 only in that the step of preparing the porous metal-based organic hybrid layer further comprises preparing a metal oxide layer by controlling the temperature in the deposition chamber at 200°C, using trimethylaluminum as the metal precursor and water as the oxidizing agent. A single deposition cycle comprises: introducing trimethylaluminum into the deposition chamber for 2s, then purging with argon for 30s, then introducing water vapor for 3s, then purging with argon for 60s, and the flow rate of all gases is controlled at 2000sccm. The number of deposition cycles of the porous metal-based organic hybrid layer is 250, and after each deposition cycle of the porous metal-based organic hybrid layer, one deposition cycle of the metal oxide layer is performed immediately thereafter, and the porous metal-based organic hybrid layer and the metal oxide layer together form the antireflection enhancement layer.

[0373] Example 1.9

[0374] Example 1.9 differs from Example 1.8 only in that after each deposition cycle of the porous metal-based organic hybrid layer, two deposition cycles of the metal oxide layer are performed immediately thereafter.

[0375] Example 1.10

[0376] Example 1.10 differs from Example 1.8 only in that after each deposition cycle of the porous metal-based organic hybrid layer, five deposition cycles of the metal oxide layer are performed immediately thereafter.

[0377] Example 1.11

[0378] Example 1.11 differs from Example 1.8 only in that after each deposition cycle of the porous metal-based organic hybrid layer, ten deposition cycles of the metal oxide layer are performed immediately thereafter.

[0379] Example 1.12

[0380] Example 1.12 differs from Example 1.8 only in that in the step of preparing the porous metal-based organic hybrid layer, diethylzinc is used as the metal precursor; and in the step of preparing the metal oxide layer, diethylzinc is used as the metal precursor.

[0381] Example 1.13

[0382] Example 1.13 differs from Example 1.8 only in that in the step of preparing the porous metal-based organic hybrid layer, titanium tetrachloride is used as the metal precursor; and in the step of preparing the metal oxide layer, titanium tetrachloride is used as the metal precursor.

[0383] Test 1: The thickness, pore size, porosity, and equivalent refractive index of each antireflection enhancement layer prepared in Examples 1.1-1.11 above were tested, and the results are shown in Table 2.

[0384] Table 2

[0385] The "~" in Table 2 represents an approximate number.

[0386] According to Table 2, the pore diameter and porosity of the antireflection enhancement layer in the present disclosure can be controlled by the number of deposition, deposition temperature and superposition of different thickness of metal oxide layer in the preparation process, which is conducive to the formation of antireflection enhancement layers with different equivalent refractive indexes, and further realizes the preparation of an antireflection enhancement layer with variable refractive index. In general, with the increase of the deposition cycle, the thickness of the porous metal-based organic hybrid layer gradually increases, and the pore diameter and porosity show a trend of first increasing and then slightly decreasing. The change trend of the equivalent refractive index is opposite to that of the pore diameter and porosity, showing a trend of first decreasing and then slightly increasing. With the increase of the deposition temperature, the pore diameter and porosity show a trend of first slightly increasing and then slightly decreasing, and the equivalent refractive index shows a trend of first slightly decreasing and then slightly increasing.

[0387] For example, referring to Table 2, the number of deposition cycles in the step of preparing the porous metal-based organic hybrid layer is different in Example 1.1-Example 1.4, and accordingly the thickness, pore diameter and porosity of the porous metal-based organic hybrid layer prepared are also different. The number of deposition cycles of Example 1.1 is more than that of Example 1.2 and Example 1.3, and accordingly the porosity and pore diameter of Example 1.1 are higher, and the equivalent refractive index is lower. The number of deposition cycles of Example 1.4 is higher than that of Example 1.1, but compared with Example 1.1, the porosity and pore diameter of Example 1.4 are slightly lower, and the equivalent refractive index is slightly higher. This may be due to the excessive deposition cycles, which will cause the subsequent deposition of metal-based organic hybrid material to block the pores to some extent.

[0388] Referring to Table 2, the deposition temperature in the step of preparing the porous metal-based organic hybrid layer is different in Example 1.1 and Example 1.5-Example 1.7. The deposition temperature of Example 1.5 is only 150°C, and its pore diameter and porosity are obviously low. The deposition temperature of Example 1.6 is 250°C, and its pore diameter and porosity are close to those of Example 1.1. The deposition temperature of Example 1.7 is further increased to 300°C, and its pore diameter and porosity are also obviously lower than those of Example 1.1.

[0389] Referring to Table 2, compared with Example 1.1, metal oxide layers are also prepared in Examples 1.8-1.11. With the increase of the deposition amount of the metal oxide layer, the pore size of the antireflection enhancement layer as a whole gradually decreases, and the porosity gradually decreases. Correspondingly, the equivalent refractive index gradually increases. The antireflection enhancement layer prepared in Example 1.11 gradually approaches the refractive index of the aluminum oxide crystal material, at this time the antireflection enhancement layer has basically lost the porous structure, and also basically does not have the effect of enhancing the antireflection effect.

[0390] Example 2.1

[0391] K9 glass is used as a substrate, and the substrate is sequentially cleaned with ethanol and ultrapure water by ultrasonic cleaning, and then dried for standby.

[0392] Preparation of an antireflection base layer: the substrate is placed in a deposition chamber, and the following thin films are sequentially deposited by atomic layer deposition:

[0393] (1) a titanium dioxide film with a thickness of 12.5 nm and a refractive index of 2.31;

[0394] (2) a silicon dioxide film with a thickness of 89 nm and a refractive index of 1.45.

[0395] Preparation of an antireflection enhancement layer on the surface of the antireflection base layer as in Example 1.1.

[0396] Example 2.2

[0397] K9 glass is used as a substrate, and the substrate is sequentially cleaned with ethanol and ultrapure water by ultrasonic cleaning, and then dried for standby.

[0398] Preparation of an antireflection base layer: the substrate is placed in a deposition chamber, and the following thin films are sequentially deposited by atomic layer deposition:

[0399] (1) an aluminum oxide film with a thickness of 12.5 nm and a refractive index of 1.62;

[0400] (2) a silicon dioxide film with a thickness of 44 nm and a refractive index of 1.45;

[0401] (3) a titanium dioxide film with a thickness of 2.8 nm and a refractive index of 2.31;

[0402] (4) a silicon dioxide film with a thickness of 42 nm and a refractive index of 1.45.

[0403] Preparation of an antireflection enhancement layer on the surface of the antireflection base layer as in Example 1.8.

[0404] Example 2.3

[0405] K9 glass is used as a substrate, and the substrate is sequentially cleaned with ethanol and ultrapure water by ultrasonic cleaning, and then dried for standby.

[0406] Preparation of antireflection base layer: The substrate was placed in a deposition chamber, and the following thin films were sequentially deposited by atomic layer deposition:

[0407] (1) a silicon dioxide thin film having a thickness of 110 nm and a refractive index of 1.45;

[0408] (2) a titanium dioxide thin film having a thickness of 10.5 nm and a refractive index of 2.31;

[0409] (3) a silicon dioxide thin film having a thickness of 35.5 nm and a refractive index of 1.45;

[0410] (4) a titanium dioxide thin film having a thickness of 113 nm and a refractive index of 2.31;

[0411] (5) a silicon dioxide thin film having a thickness of 43 nm and a refractive index of 1.45;

[0412] (6) a titanium dioxide thin film having a thickness of 21 nm and a refractive index of 2.31;

[0413] (7) a silicon dioxide thin film having a thickness of 42 nm and a refractive index of 1.45;

[0414] (8) a titanium dioxide thin film having a thickness of 108 nm and a refractive index of 2.31;

[0415] (9) a magnesium fluoride thin film having a thickness of 87.5 nm and a refractive index of 1.38.

[0416] Preparation of antireflection enhancement layer on the surface of the antireflection base layer as in Example 1.8.

[0417] Comparative Example 2

[0418] The difference between Comparative Example 2 and Example 2.1 is only that Comparative Example 2 does not prepare an antireflection enhancement layer.

[0419] Comparative Example 3

[0420] The difference between Comparative Example 3 and Example 2.2 is only that Comparative Example 3 does not prepare an antireflection enhancement layer.

[0421] Comparative Example 4

[0422] The difference between Comparative Example 4 and Example 2.3 is only that Comparative Example 4 does not prepare an antireflection enhancement layer.

[0423] Test 2: The reflectance of the coated glasses of Example 2.1, Example 2.2 and Comparative Example 4 for light in the wavelength range of 400 nm to 800 nm was tested. The results are shown in Table 3. Figure 12 shows a graph of the reflectance of the coated glass of Comparative Example 4 as a function of wavelength, and Figure 13 shows a graph of the reflectance of the coated glasses of Example 2.1 and Example 2.2 as a function of wavelength.

[0424] Table 3

[0425] Comparative Examples 2 to 4 did not include the anti-reflective enhancement layer. As shown in Table 3, the average reflectance of the coated glasses decreased as the number of layers in the anti-reflective base layer increased, but even with a 9 layer anti-reflective base layer, the average reflectance of the coated glass was still 0.53%. As shown in Figure 12, the reflectance of the coated glass of Comparative Example 4 was generally below 1%, but the transmittance of the coated glass for light in some wavelength ranges was still above 0.5%.

[0426] Examples 2.1 to 2.3 included the anti-reflective enhancement layer of the present disclosure. As shown in Table 3, the average reflectance of the coated glasses of Examples 2.1 to 2.3 was significantly lower than the average reflectance of the coated glasses of Comparative Examples 2 to 4. More importantly, even compared to Comparative Example 4, which had a more complex anti-reflective base layer structure, Examples 2.1 and 2.2, which had a simpler anti-reflective base layer structure, still exhibited lower reflectance. As shown in Figure 13, the reflectance of the coated glasses of Examples 2.1 and 2.2 was below 0.2%. These results demonstrate that the anti-reflective coated glass of the present disclosure can have a simplified anti-reflective structure while still having low reflectance.

[0427] It should be noted that the above examples are for illustrative purposes only and are not meant to limit the present disclosure.

[0428] It should be understood that, unless otherwise explicitly specified herein, the order of execution of the steps is not strictly limited and the steps can be executed in other orders. Moreover, at least some of the steps in the preparation process can include multiple sub-steps or stages, which can not necessarily be executed at the same time, but can be executed at different times, and the order of execution of the sub-steps or stages can not necessarily be sequential, but can be executed in rotation or alternation with at least some of the other steps or sub-steps or stages of other steps.

[0429] Each of the embodiments in the present specification is described in a progressive manner, and each embodiment focuses on the differences from other embodiments. The same or similar parts between the embodiments can be mutually referred to.

[0430] The technical features of the above embodiments can be combined in any manner. For the sake of brevity, not all possible combinations of the technical features described above are described, however, it is to be understood that any combination of the technical features is within the scope of the present specification, as long as the combination is not contradictory.

Claims

1. An optical device, characterized by The workpiece body and the porous film arranged on the workpiece body are provided, and the porous film is used to reduce the reflected light on the workpiece body, and the porous film comprises a porous metal oxide layer or a porous metal-based organic hybrid layer.

2. The optical device of claim 1, wherein, The porous metal oxide layer satisfies at least one of the following characteristics: (1) the thickness of the porous metal oxide layer is 40-100 nm; (2) the pore size of the pores in the porous metal oxide layer is 35-105 nm; (3) the average light transmittance of the porous film on which the porous metal oxide layer is arranged in the 450-675 nm wave band is more than 99%.

3. The optical device according to claim 1 or 2, characterized in that The porous film comprising the porous metal oxide layer further comprises a shape-retaining layer attached to the pore structure of the porous metal oxide layer.

4. The optical device of claim 3, wherein, The shape-retaining layer satisfies at least one of the following characteristics: (1) the material of the shape-retaining layer is selected from oxides, and the shape-retaining layer is prepared by one or more of atomic layer deposition, molecular layer deposition, chemical vapor deposition, physical vapor deposition and liquid phase epitaxy; (2) the material of the shape-retaining layer is selected from one or more of silicon oxide, aluminum oxide and titanium oxide; (3) the thickness of the shape-retaining layer is ≤10 nm.

5. The optical device of claim 1, wherein, The porous metal-based organic hybrid layer satisfies at least one of the following characteristics: (1) the material of the porous metal-based organic hybrid layer comprises one or more of an aluminum-based hydroquinone hybrid material, a zinc-based hydroquinone hybrid material and a titanium-based hydroquinone hybrid material; (2) the porous metal-based organic hybrid layer is prepared by molecular layer deposition; (3) the raw materials for preparing the porous metal-based organic hybrid layer comprise a first metal precursor and an organic precursor; wherein, the first metal precursor is selected from one or more of trimethylaluminum, zinc bisethylenate and titanium tetrachloride, and the organic precursor is hydroquinone.

6. The optical device according to claim 1 or 5, characterized in that The porous film comprises the porous metal-based organic hybrid layer, and the porous metal-based organic hybrid layer constitutes an anti-reflection enhancement layer; or The porous film comprises the porous metal-based organic hybrid layer and further comprises a metal oxide layer, the material of the metal oxide layer comprises a metal oxide, the porous metal-based organic hybrid layer and the metal oxide layer constitute an anti-reflection enhancement layer, the number of layers of the porous metal-based organic hybrid layer and the metal oxide layer is at least one, and the porous metal-based organic hybrid layer and the metal oxide layer are alternately stacked.

7. The optical device of claim 6, wherein, The metal oxide layer satisfies at least one of the following characteristics: (1) the material of the metal oxide layer comprises one or more of aluminum oxide, zinc oxide and titanium oxide; (2) the metal oxide layer is prepared by atomic layer deposition.

8. The optical device according to claim 6 or 7, characterized in that The equivalent refractive index of the anti-reflection enhancement layer as a whole is 1.2-1.

5.

9. The optical device according to any one of claims 6 to 8, characterized in that The anti-reflection enhancement layer satisfies at least one of the following characteristics: (1) the thickness of the anti-reflection enhancement layer is 10-200 nm; (2) the pore size of the pores in the anti-reflection enhancement layer is 1-30 nm; (3) the porosity of the anti-reflection enhancement layer is 10%-70%.

10. The optical device according to any one of claims 6 to 9, characterized in that The porous film further comprises an antireflection base layer, the antireflection base layer is arranged in a stack with the antireflection enhancement layer, and the antireflection base layer and the antireflection enhancement layer form an antireflection structure.

11. The optical device of claim 10, wherein, The antireflection base layer comprises a high-refractive-index film and a low-refractive-index film, the refractive index of the high-refractive-index film is higher than the refractive index of 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 arranged in an alternating stack.

12. The optical device of claim 11, wherein, The total number of layers of the high-refractive-index film and the low-refractive-index film is 2 to 4.

13. The optical device according to any one of claims 10 to 12, characterized in that The average reflectivity of the antireflection structure for light in a wavelength range of 400 nm to 800 nm is less than or equal to 0.2%.

14. A method of manufacturing an optical device, characterized by, The method comprises the following steps: Preparation of a porous film, the preparation method of the porous film comprising a molecular deposition method, the porous film comprising a porous metal oxide layer or a porous metal-based organic hybrid layer, the porous film being used to reduce reflected light on the workpiece body; The porous film is arranged on the workpiece body.

15. The method of producing an optical device according to claim 14, wherein The porous film comprises a porous metal oxide layer, and the preparation method of the porous film comprises the following steps: Preparation of at least one first precursor monolayer and at least one second precursor monolayer on a substrate, the material of the first precursor monolayer and the material of the second precursor monolayer being capable of forming a hydrolysable metal organic composite layer after reaction; The metal organic composite layer is placed in an aqueous environment to perform a hydrolysis reaction, so that the metal organic composite layer is converted to form the porous metal oxide layer.

16. The method of producing an optical device according to claim 15, wherein The preparation method of the porous film further comprises the following steps: Preparation of the shape-preserving layer on the porous metal oxide layer for reinforcing the porous metal oxide layer.

17. The method of producing an optical device according to claim 16, wherein The shape-preserving layer is prepared by one or more of atomic layer deposition, molecular layer deposition, chemical vapor deposition, physical vapor deposition, and liquid phase epitaxy.

18. A method of manufacturing an optical device according to claim 16 or 17, characterized in that, Before the preparation of the shape-preserving layer, the porous metal oxide layer is subjected to a shaping treatment.

19. The method of producing an optical device according to claim 18, wherein The shaping treatment of the porous metal oxide layer comprises placing the porous metal oxide layer in a protective gas environment and heating the porous metal oxide layer.

20. The method of producing an optical device according to claim 19, wherein The heating of the porous metal oxide layer satisfies at least one of the following characteristics: (1) the heating temperature is 50°C to 80°C; (2) the heating time is 5 min to 10 min.

21. A method of producing an optical device according to any one of claims 15 to 20, characterized in that, The hydrolysis reaction satisfies at least one of the following characteristics: (1) the temperature of the hydrolysis reaction is 10°C to 80°C; (2) the time of the hydrolysis reaction is 5 min to 120 min.

22. A method of producing an optical device according to any one of claims 15 to 20, characterized in that, The thickness of the formed metal organic composite layer is 5 nm to 60 nm.

23. A method of producing an optical device according to any one of claims 15 to 20, characterized in that, The steps of preparing the first precursor monolayer and the second precursor monolayer on the substrate comprise: Placing the substrate in a deposition chamber; Introducing the material of the first precursor monolayer into the deposition chamber and allowing it to adhere to the substrate to form the first precursor monolayer; Introducing the material of the second precursor monolayer into the deposition chamber and allowing it to adhere to the substrate to form the second precursor monolayer; and The step of forming the first precursor monolayer and the step of forming the second precursor monolayer are repeated as one deposition cycle, and the deposition cycle is repeated for multiple times.

24. A method for producing an optical device according to any one of claims 15 to 20, characterized in that, The metal-organic composite layer comprises an aluminum-based organic-inorganic hybrid material; the material of the first precursor monolayer comprises a metal-organic compound, and the material of the second precursor monolayer comprises an alcohol-based organic compound and / or a derivative thereof.

25. The method of producing an optical device according to claim 24, wherein The material of the first precursor monolayer comprises trimethylaluminum, and the material of the second precursor monolayer comprises one or more of ethylene glycol, glycerol and ethanolamine.

26. A method of producing an optical device according to any one of claims 15 to 25, characterized in that, The process of preparing the first precursor monolayer and the second precursor monolayer on the substrate satisfies at least one of the following characteristics: (1) the number of the deposition cycle is 15-100 times; (2) the temperature of the deposition chamber is 50-200℃.

27. The method of producing an optical device according to claim 14, wherein The porous membrane comprises a porous metal-based organic hybrid layer, and a preparation method of the porous membrane comprises the following steps: The porous metal-based organic hybrid layer is formed by using a molecular layer deposition method.

28. The method of producing an optical device according to claim 27, wherein The material of the porous metal-based organic hybrid layer comprises one or more of an aluminum-based hydroquinone hybrid material, a zinc-based hydroquinone hybrid material and a titanium-based hydroquinone hybrid material.

29. A method of producing an optical device according to any one of claims 27 to 28, characterised in that, The preparation method of the porous membrane further comprises the following steps: forming a metal oxide layer by deposition, and the step of forming the porous metal-based organic hybrid layer and the step of forming the metal oxide layer are alternately performed.

30. The method of producing an optical device according to claim 29, wherein The step of forming the porous metal-based organic hybrid layer comprises: introducing a first metal precursor into a deposition chamber and allowing the first metal precursor to adhere to a substrate to form a first monolayer, introducing an organic precursor into the deposition chamber and allowing the organic precursor to adhere to the substrate to form a second monolayer; The step of forming the metal oxide layer comprises: introducing a second metal precursor into the deposition chamber and allowing the second metal precursor to adhere to the substrate to form a third monolayer, introducing an oxidizing agent into the deposition chamber and allowing the oxidizing agent to adhere to the substrate to form a fourth monolayer; The step of forming the first monolayer and the step of forming the second monolayer are collectively regarded as one first deposition cycle, and the step of forming the third monolayer and the step of forming the fourth monolayer are collectively regarded as one second deposition cycle; At least one first deposition cycle is continuously performed to form one layer of the porous metal-based organic hybrid layer, and at least one second deposition cycle is continuously performed to form one layer of the metal oxide layer, and at least one layer of the porous metal-based organic hybrid layer and at least one layer of the metal oxide layer are alternately formed.

31. The method of producing an optical device according to claim 30, wherein The first metal precursor is selected from one or more of trimethylaluminum, zinc ethylene and titanium tetrachloride, and the organic precursor is selected from hydroquinone.

32. A method of producing an optical device according to any one of claims 30 to 31, characterised in that, The second metal precursor is selected from one or more of trimethylaluminum, zinc ethylene and titanium tetrachloride, and the oxidizing agent is selected from one or more of water and ozone.

33. A method of producing an optical device according to any one of claims 30 to 32, characterised in that, The ratio of the number of the first deposition cycle to the number of the second deposition cycle is 1:(1-5).

34. A method of producing an optical device according to any one of claims 30 to 33, characterised in that, The number of the first deposition cycle is 40-500 times.

35. A method of producing an optical device according to any one of claims 27 to 34, characterised in that, In the step of depositing the porous metal-based organic hybrid layer, the temperature of the deposition chamber is controlled to be 150-300°C.

36. A method of producing an optical device according to any one of claims 27 to 35, characterised in that, The method for preparing the porous film comprises the following steps: providing the substrate; preparing an anti-reflective base layer on the substrate; placing the substrate in a deposition chamber to prepare an anti-reflective enhancement layer on the substrate, wherein the step of preparing the anti-reflective enhancement layer comprises depositing the porous metal-based organic hybrid layer; or the step of preparing the anti-reflective enhancement layer comprises depositing the porous metal-based organic hybrid layer and depositing the metal oxide layer, and the step of depositing the porous metal-based organic hybrid layer and the step of depositing the metal oxide layer are performed alternately.

37. The method of producing an optical device according to claim 36, wherein The method for preparing the anti-reflective base layer on the substrate comprises the following steps: alternately depositing high-refractive-index films and low-refractive-index films on the substrate, the refractive index of the high-refractive-index films being higher than that of the low-refractive-index films, and each of the high-refractive-index films and the low-refractive-index films having at least one layer.

38. Use of a porous film in an antireflective film for optical devices, characterized in that, The porous film comprises a porous metal oxide layer or a porous metal-based organic hybrid layer.

39. The use according to claim 38, wherein The method for preparing the porous film comprises molecular layer deposition.

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