CN221668065U

CN221668065U - Optical composite film layer

Info

Publication number: CN221668065U
Application number: CN202420325330.7U
Authority: CN
Inventors: 唐智; 陈豪; 徐瑶
Original assignee: Nafeng Vacuum Coating Shanghai Co ltd
Current assignee: Nafeng Vacuum Coating Shanghai Co ltd
Priority date: 2024-02-21
Filing date: 2024-02-21
Publication date: 2024-09-06
Anticipated expiration: 2034-02-21

Abstract

The utility model discloses an optical composite film layer, which comprises: the first antireflection film layer, the protective film layer and the AF film layer are sequentially overlapped on the first surface of the substrate; the first anti-reflection film layer comprises an alternating layer stack of a first low refractive index film layer and a first high refractive index film layer, and the protective film layer comprises a first amorphous carbon film layer. The utility model can realize good visual effect of enabling the whole optical composite film layer to present neutral color without sacrificing optical performance while meeting the requirements of anti-reflection and guaranteeing wear resistance.

Description

Optical composite film layer

Technical Field

The utility model relates to the technical field of optical coatings, in particular to an optical composite film layer.

Background

An AR film (anti-reflection or anti-reflection film) is a surface optical plating layer that increases the transmittance of light by reducing the reflection of light. It can improve contrast by reducing scattered light in the system, such as a telescope. Many AR coatings include transparent thin film structures with different refractive indices. The thickness of the film determines the wavelength of the reflected light that it acts upon. The principle of AR is that when light is secondarily reflected on an AR film, interference with the original reflected light occurs, so that the reflected light is weakened, and the energy of the light is not changed according to energy conservation, so that when the reflected light is reduced, the transmitted light is increased.

The application field of the AR film is wide, such as the fields of solar cell modules, photo-thermal, buildings, automobile glass and the like, and the AR film is generally related to optics. At present, on a display panel closely related to life, the transmittance of the display panel can be improved and the reflectivity can be reduced by an AR film. However, the wear-resisting performance of the materials commonly used for the AR film is poor, and external friction and scratch are often encountered, so that scratches appear on the surface, and the use effect is affected. It is highly desirable to increase the durability and extend the life of the product.

The existing super wear-resistant AR film generally uses materials with high hardness such as SiN to increase the hardness of the film layer, but the wear resistance is not greatly improved due to the limitation of the material characteristics. Meanwhile, the bottleneck brought by the high-hardness AR film layer material cannot realize very good wear resistance. In addition, when an AR film is coated on a mobile phone screen or glass, a certain layer of the AR film is required to reach a certain thickness in order to achieve a better wear resistance, and the control of the thickness of the film layer is limited, so that the optical performance of the color neutrality (the color neutrality refers to that the color does not belong to a cool tone or a warm tone and is a relatively independent color) is sacrificed, and even if the color of the film layer is transparent, the problem of bluish or greenish or even color emission often occurs, thereby influencing the visual effect.

In addition, in some special applications with low requirements on reflectivity and transmittance, such as vehicle-mounted screens, the functional surfaces of the vehicle-mounted screens also need to be protected, and wear-resistant requirements also exist. If the conventional AR film is adopted for protection, the protection is unnecessary, and meanwhile, the protection cannot realize better wear resistance, and the actual protection effect is difficult to realize.

Disclosure of utility model

The utility model aims to overcome the defects in the prior art and provide an optical composite film.

In order to achieve the above purpose, the technical scheme of the utility model is as follows:

the utility model provides an optical composite film layer, comprising:

The first antireflection film layer, the protective film layer and the AF film layer are sequentially overlapped on the first surface of the substrate;

The first anti-reflection film layer comprises an alternating layer stack of a first low refractive index film layer and a first high refractive index film layer, and the protective film layer comprises a first amorphous carbon film layer.

Further, the refractive index of the first low refractive index film layer is smaller than that of the first high refractive index film layer, a first bottom film layer closest to the substrate in the first anti-reflection film layers is the first low refractive index film layer, and a first top film layer farthest from the substrate in the first anti-reflection film layers is the first low refractive index film layer or the first high refractive index film layer.

Further, a first transition protective film layer is further arranged between the protective film layer and the first anti-reflection film layer, and the first transition protective film layer comprises a second amorphous carbon film layer.

Further, the protection film layer has a first film layer structure in which additional ionized gas elements are distributed in the first amorphous carbon film layer, the first transition protection film layer has a second film layer structure in which additional ionized gas elements and first compounds are distributed in the second amorphous carbon film layer, the first compounds are in contact with the surface of the first top film layer at the interface of the first transition protection film layer and the first antireflection film layer, and the first compounds are the first top film layer material.

Further, the first anti-reflection film layer is provided with a third film layer structure in which the additional second amorphous carbon film layer material is distributed in the first top film layer, and the second amorphous carbon film layer material distributed in the first top film layer is in contact with the surface of the second amorphous carbon film layer at the interface of the first anti-reflection film layer and the first transition protection film layer.

Further, a second transition protective film layer is further arranged between the protective film layer and the AF film layer, and the second transition protective film layer comprises a third amorphous carbon film layer.

Further, the second transition protective film layer has a fourth film layer structure in which additional ionized gas elements are distributed in the third amorphous carbon film layer, or the second transition protective film layer has a fourth film layer structure in which additional ionized gas elements and a second compound are distributed in the third amorphous carbon film layer, and the second compound is in contact with the surface of the AF film layer at the interface of the second transition protective film layer and the AF film layer.

Further, the first, second, and third amorphous carbon film layers include DLC film layers, or the first, second, and third amorphous carbon film layers include TA-C film layers; the ionized gas elements added in the first amorphous carbon film layer, the ionized gas elements added in the second amorphous carbon film layer and the ionized gas elements added in the third amorphous carbon film layer comprise ionized hydrogen elements.

Further, the method further comprises the following steps: the second antireflection film layer is arranged on a second surface of the substrate opposite to the first surface, the second antireflection film layer comprises alternating layers of second low-refractive-index film layers and second high-refractive-index film layers, the refractive index of the second low-refractive-index film layers is smaller than that of the second high-refractive-index film layers, a second bottom film layer closest to the substrate in the second antireflection film layers is the second low-refractive-index film layer, and a second top film layer farthest from the substrate in the second antireflection film layers is the second low-refractive-index film layer.

Further, another implementation manner of the optical composite film layer is that at least one of the first antireflection film layer and the second antireflection film layer is not provided.

According to the technical scheme, the first anti-reflection film layer, the protective film layer and the AF film layer are sequentially formed on the substrate, so that the first anti-reflection film layer comprises the alternating layers of the first low-refractive-index film layer and the first high-refractive-index film layer, the protective film layer comprises the first amorphous carbon film layer, and the first anti-reflection film layer can be protected by utilizing the higher hardness and good wear resistance of an amorphous carbon material (such as DLC or TA-C) per se, so that the overall wear resistance of the optical composite film layer is improved. Further, by providing the protective film layer with the first film layer structure in which the additional ionized gas elements (such as hydrogen) are distributed in the first amorphous carbon film layer, the thickness of the film layer can be reduced, the hardness can be improved, the overall optical composite film layer can achieve an ultrahigh wear resistance effect, and the optical composite film layer has good optical performance (light transmittance is improved, reflection is reduced, and neutral color is maintained); the first transition protective film layer comprising the second amorphous carbon film layer is further formed between the first anti-reflection film layer and the protective film layer, ionized gas elements and first compound (first top film layer) materials are added into the second amorphous carbon film layer, the second amorphous carbon film layer materials are added into the first top film layer of the first anti-reflection film layer, a second transition protective film layer comprising the third amorphous carbon film layer is formed between the protective film layer and the AF film layer, ionized gas elements (and second compound) materials are added into the third amorphous carbon film layer, and the ionized gas elements (and second compound) materials are added into the third amorphous carbon film layer, so that the anti-reflection effect of the whole optical composite film layer is achieved through cooperation with the protective film layer, the optical and mechanical properties of the whole optical composite film layer can be further optimized, the defects that the AR film under the traditional method can influence and change the appearance color (bluing, greening or even color developing) are overcome, and the whole optical composite film can realize the good visual effect without sacrificing the optical properties while the wear resistance is ensured. The optical composite film layer of the utility model can be applied to various glass substrates including, but not limited to, metals, plastics, resins and the like, thereby achieving the desired anti-reflection effect.

Drawings

Fig. 1 is a schematic structural diagram of an optical composite film layer with a first anti-reflection film layer, a protective film layer and an AF film layer sequentially disposed on a single surface of a substrate according to a preferred embodiment of the present utility model.

Fig. 2 is a schematic structural diagram of an optical composite film layer with a first anti-reflection film layer, a first transition protective film layer, a protective film layer and an AF film layer sequentially disposed on a single surface of a substrate according to a preferred embodiment of the present utility model.

Fig. 3 is a schematic structural diagram of an optical composite film layer with a first anti-reflection film layer, a first transition protective film layer, a second transition protective film layer and an AF film layer sequentially disposed on a single surface of a substrate according to a preferred embodiment of the present utility model.

Fig. 4 is a schematic structural diagram of an optical composite film layer with a first antireflection film layer, a first transitional protective film layer, a second transitional protective film layer and an AF film layer sequentially disposed on a first surface of a substrate, and a second antireflection film layer disposed on a second surface of the substrate according to a preferred embodiment of the present utility model.

Fig. 5 is a schematic structural diagram of an optical composite film with a protective film and an AF film sequentially disposed on a first surface of a substrate and a second antireflection film disposed on a second surface of the substrate according to a preferred embodiment of the present utility model.

Fig. 6 is a schematic structural diagram of an optical composite film layer with a protective film layer and an AF film layer sequentially disposed on a single surface of a substrate according to a preferred embodiment of the present utility model.

Fig. 7 is a schematic structural view of an optical composite film layer of the comparative example.

Detailed Description

For the purpose of making the objects, technical solutions and advantages of the embodiments of the present utility model more apparent, the technical solutions in the embodiments of the present utility model will be clearly and completely described below, and it is apparent that the described embodiments are some embodiments of the present utility model, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the utility model without making any inventive effort, are intended to be within the scope of the utility model. Unless otherwise defined, technical or scientific terms used herein should be given the ordinary meaning as understood by one of ordinary skill in the art to which this utility model belongs. As used herein, the word "comprising" and the like means that elements or items preceding the word are included in the element or item listed after the word and equivalents thereof without precluding other elements or items.

The following describes the embodiments of the present utility model in further detail with reference to the accompanying drawings.

Reference is made to fig. 1. An optical composite film of the present utility model includes a first antireflection film 11, a protective film 12, and an AF film 13 (anti-fingerprint film) sequentially stacked on a first surface (shown as an upper surface, the same applies hereinafter) of a substrate 10. Wherein the first anti-reflection film layer 11 comprises an alternating layer stack of a first low refractive index film layer and a first high refractive index film layer. The protective film layer 12 includes a first amorphous carbon film layer 121.

Further, the refractive index of the first low refractive index film layer (L) is smaller than the refractive index of the first high refractive index film layer (H). In addition, the first bottom layer 111 closest to the substrate 10 in the first anti-reflection film 11 is a first low refractive index film, and the first top layer 112 farthest from the substrate 10 in the first anti-reflection film 11 is a first low refractive index film, so that the anti-reflection effect is optimal.

Of course, according to actual performance requirements, the first bottom layer film closest to the substrate in the first anti-reflection film layer may be set as a first low refractive index film layer, and the first top layer film farthest from the substrate in the first anti-reflection film layer may be set as a first high refractive index film layer.

In some embodiments, the first low refractive index film material comprises a common low refractive index optical material having a composition of NaAlF, mgF, alO, or SiO, or the like. The first high refractive index film material comprises a common high refractive index optical material with a composition of TiO, siN or NbO.

In some embodiments, the number of stacked layers of the alternate layers in the first antireflection film layer 11 is 1 to 22, and each layer has a thickness of 10 to 200nm. Preferably, the number of layers of the alternate layers is 5 to 8; the thickness of each layer is 20-80 nm. When the number of the above-described lamination layers is 1, the first antireflection film layer 11 will have only a single first low refractive index film layer.

In some embodiments, the first amorphous carbon film layer 121 includes a DLC (diamond like carbon) film layer.

In some embodiments, the first amorphous carbon film layer 121 includes a TA-C (tetrahedral amorphous carbon) film layer.

The AF film layer 13 is the uppermost film layer of the optical composite film layer, contacting air. The material of the AF film layer 13 is generally a silicon-fluorine product with hydrophobic and oleophobic properties, such as heptadecafluorodecyl trimethoxysilane, etc. The AF film layer 13 is arranged on the protective film layer 12, so that the anti-fingerprint function of water and oil repellency can be well achieved, and the use feeling is improved.

Reference is made to fig. 2. In some embodiments, in an optical composite film according to the present utility model, on the basis of fig. 1, a first transitional protection film layer 14 is further disposed between the protection film layer 12 and the first anti-reflection film layer 11, and the first transitional protection film layer 14 includes a second amorphous carbon film layer 141. The second amorphous carbon film 141 includes a DLC film or a TA-C film. When the first amorphous carbon film layer 121 is a DLC film layer, the second amorphous carbon film layer 141 is also a DLC film layer. When the first amorphous carbon film 121 is a TA-C film, the second amorphous carbon film 141 is also a TA-C film.

In some embodiments, the protective film 12 has a first film structure in which the additional ionized gas elements are distributed in the first amorphous carbon film 121. The first transition protective film layer 14 has a second film layer structure in which additional ionized gas elements and first compounds are distributed in the second amorphous carbon film layer 141, and the first compounds are in contact with the surface of the first top film layer 112 at the interface of the first transition protective film layer 14 and the first anti-reflection film layer 11. The first compound is the first top layer 112 material.

Further, the first anti-reflection film 11 has a third film structure in which an additional second amorphous carbon film 141 material is distributed in the first top film 112, and the second amorphous carbon film 141 material distributed in the first top film 112 contacts with the surface of the second amorphous carbon film 141 at the interface between the first anti-reflection film 11 and the first transition protection film 14.

In some embodiments, the ionized gas element may be, for example, ionized hydrogen element, and may be added to the first amorphous carbon film 121 of the protective film 12 by, for example, doping. By adding a certain proportion of hydrogen into the first amorphous carbon film 121, the hardness and wear resistance of the protective film 12 can be obviously improved, so that the protective film 12 has a reinforced first film structure. At the same time, the protective film 12 can achieve better optical performance.

Taking the material of the first amorphous carbon film 121 of the protective film 12 as TA-C as an example, although the conventional TA-C has better wear resistance, the conventional TA-C has poor optical performance, and the film has large absorption, and can affect the transmission performance of the product in the optical application field, so that the conventional TA-C cannot be applied to display panel glass such as mobile phone flat panel and the like. The TA-C material of the protective film 12 is doped with hydrogen, so that the TA-C film has excellent wear resistance and can reduce absorption, thereby meeting the optical application.

For example, on quartz glass, the doped TA-C film layer with the thickness of 4nm is prepared, the absorption can reach 0.5-1.5% in the visible light range, and the single-sided reflectivity can reach 1-2%. However, if undoped TA-C films of the same 4nm thickness were prepared on quartz glass, the absorption would reach 6% and above, and the single-sided reflectivity would typically increase to 3% and above. Thus, the present invention allows the optical and mechanical properties of the protective film 12 to be optimized by doping it.

In some embodiments, ionized gaseous elemental hydrogen and first top layer 112 material (first compound) may be added to the second amorphous carbon layer 141 of the first transitional protective film 14, for example, by doping. And adding the second amorphous carbon film 141 material into the first top film 112 of the first anti-reflection film 11 by doping, for example. Wherein, the material of the first top layer 112 added in the second amorphous carbon film 141 contacts with the upper surface of the first top layer 112 at the interface between the second amorphous carbon film 141 and the first top layer 112. The second amorphous carbon film layer 141 material added in the first top film layer 112 contacts with the lower surface of the second amorphous carbon film layer 141 at the interface of the first top film layer 112 and the second amorphous carbon film layer 141. For example, when the material of the first top film layer 112 is silicon dioxide and the second amorphous carbon film layer 141 is a TA-C film layer, TA-C is doped in the first top film layer 112, and hydrogen and silicon dioxide are doped in the second amorphous carbon film layer 141.

By additionally adding a certain proportion of hydrogen and a first top layer film 112 material into the second amorphous carbon film 141, the hardness and wear resistance of the first transition protective film 14 are improved, and meanwhile, the bonding force between the first transition protective film 14 and the first anti-reflection film 11 can be enhanced, so that the third film structure and the second film structure become reinforced film structures which can be matched with the first film structure of the protective film 12, the bonding force between the third film structure and the first transition protective film 14 is obviously improved, the overall bonding force between the inner films of the optical composite film and between the optical composite film and the substrate 10 is further improved, the first transition protective film 14 has the reinforced second film structure which can be matched with the protective film 12, an optical interface is eliminated, optical loss is reduced, and the optical composite film achieves better overall optical performance.

The third film structure is a novel film form specially designed for the protective film 12, and is used for matching with the protective film 12 to realize the antireflection of the whole optical composite film, so that a higher antireflection effect is achieved, the hardness is higher, and the abrasion resistance of the whole optical composite film can be further improved.

Reference is made to fig. 3. In some embodiments, in an optical composite film according to the present utility model, a second transitional protective film 15 is further disposed between the protective film 12 and the AF film 13 on the basis of fig. 2. The second transition protective film layer 15 includes a third amorphous carbon film layer 151.

In some embodiments, the third amorphous carbon film 151 includes a DLC film or a TA-C film. And when the first amorphous carbon film layer 121 and the second amorphous carbon film layer 141 are DLC film layers, the third amorphous carbon film layer 151 is also a DLC film layer. When the first amorphous carbon film layer 121 and the second amorphous carbon film layer 141 are TA-C film layers, the third amorphous carbon film layer 151 is also a TA-C film layer.

In some embodiments, the second transitional protection film layer 15 has a fourth film layer structure in which additional ionized gas elements are distributed in the third amorphous carbon film layer 151, so as to improve the hardness and wear resistance of the third amorphous carbon film layer 151. So that the fourth film structure becomes a reinforced film structure that can be mated with the protective film 12.

In some embodiments, the second transitional protection film layer 15 has a fourth film layer structure in which the additional ionized gas elements and the second compound are distributed in the third amorphous carbon film layer 151 to improve the hardness, wear resistance, and bonding degree of the third amorphous carbon film layer 151, and the second compound is in contact with the lower surface of the AF film layer 13 at the interface of the second transitional protection film layer 15 (the third amorphous carbon film layer 151) and the AF film layer 13. Thereby making the fourth film structure a reinforced film structure which can be matched with the protective film 12 and obviously improving the binding force between the second transition protective film 15 and the AF film 13.

The ionized gas elements added to the first amorphous carbon film 121, the ionized gas elements added to the second amorphous carbon film 141, and the ionized gas elements added to the third amorphous carbon film 151 include ionized hydrogen elements. Hydrogen or hydrogen and a second compound may be added to the third amorphous carbon film layer 151 by, for example, doping.

In some embodiments, the second compound comprises a hydride, nitride, carbide, oxide, or fluoride. For example, the second compound may be a common optical high-low refractive index material having a composition of TiO, siN, nbO, naAlF, mgF, alO, or SiO, etc.

By additionally adding a certain proportion of hydrogen and a second compound into the third amorphous carbon film 151, the hardness and the wear resistance of the second transition protective film 15 are improved, and meanwhile, the binding force between the second transition protective film 15 and the AF film 13 can be enhanced, so that the overall binding force between the optical composite film and the optical composite film is further improved. Meanwhile, the optical interface can be eliminated, the optical loss is reduced, and the optical composite film layer achieves better overall optical performance. The first anti-reflection film layer 11, the second amorphous carbon film layer 141, the first amorphous carbon film layer 121 and the third amorphous carbon film layer 151 form perfect mutual coordination, the first amorphous carbon film layer 121 (the protective film layer 12) is used as the film layer with the highest hardness, and the second amorphous carbon film layer 141 and the third amorphous carbon film layer 151 are used as transition film layers to enhance the binding force with other film layers, so that the good visual effect of enabling the whole optical composite film layer to show neutral color can be realized without sacrificing the optical performance while ensuring the wear resistance.

Refer to fig. 4. In some embodiments, an optical composite film of the present utility model further includes a second anti-reflection film 16 disposed on a second surface (lower surface, back surface) of the substrate 10 opposite to the first surface (front surface) on the basis of fig. 3.

Wherein the second anti-reflection film layer 16 comprises an alternating layer stack of a second low refractive index film layer (L) and a second high refractive index film layer (H). And, the refractive index of the second low refractive index film layer is smaller than that of the second high refractive index film layer, the second bottom film layer 161 closest to the substrate 10 in the second antireflection film layer 16 is the second low refractive index film layer, and the second top film layer 162 farthest from the substrate 10 in the second antireflection film layer 16 is the second low refractive index film layer.

In some embodiments, the second low refractive index film material comprises a common low refractive index optical material having a composition of NaAlF, mgF, alO, or SiO, or the like. The second high refractive index film material comprises a common high refractive index optical material with a composition of TiO, siN or NbO.

In some embodiments, the number of layers of the alternating layers of the second anti-reflection film layer 16 is 1 to 22, and each layer has a thickness of 10 to 200nm. Preferably, the number of layers of the alternate layers is 5 to 8; the thickness of each layer is 20-80 nm.

When the first anti-reflection film layer 11 and the second anti-reflection film layer 16 are simultaneously disposed on the front and back sides of the substrate 10, the number of stacked layers of the alternate layers of the first anti-reflection film layer 11 and the second anti-reflection film layer 16 is the same, and the first bottom film layer 111 closest to the substrate 10 in the first anti-reflection film layer 11 is the first low refractive index film layer, and the first top film layer 112 farthest from the substrate 10 in the first anti-reflection film layer 11 is the first low refractive index film layer. Moreover, the thickness of each of the respective alternate layers of the first antireflection film layer 11 and the second antireflection film layer 16 may be designed differently as needed.

Reference is made to fig. 5. In some embodiments, an optical composite film layer of the present utility model is formed by sequentially stacking a protective film layer 12 and an AF film layer 13 on a first surface of a substrate 10, and providing a second antireflection film layer 16 on a second surface of the substrate 10. I.e. only the second anti-reflection film layer 16 is provided on the substrate 10, while the first anti-reflection film layer 11 is omitted. In addition, a second amorphous carbon film layer 141 and a third amorphous carbon film layer 151 (for example, at least one of them may be added) may be added between the substrate 10 and the protective film layer 12 and between the protective film layer 12 and the AF film layer 13, respectively.

Refer to fig. 6. In some embodiments, an optical composite film layer of the present utility model is provided with a protective film layer 12 and an AF film layer 13 stacked in order on only a first surface of a substrate 10, and the first antireflection film layer 11 and the second antireflection film layer 16 are omitted. I.e. on the basis of fig. 1, the provision of the first anti-reflection film layer 11 is omitted. The optical composite film layer of the embodiment can be applied to special applications (such as vehicle-mounted screens with low requirements on reflectivity and transmittance) without arranging an antireflection film.

The embodiments of fig. 5-6 described above embody another implementation of the optical composite film layer, i.e., without at least one of the first anti-reflective film layer 11 and the second anti-reflective film layer 16.

In the above embodiments, the substrate 10 material may be glass, metal, plastic or resin including but not limited to various types.

The second amorphous carbon film 141 (first transition protective film 14) has a film thickness of 1 to 20nm, preferably 2 to 10nm; the film thickness of the first amorphous carbon film layer 121 (protective film layer 12) is 1 to 20nm, preferably 3 to 10nm; the thickness of the third amorphous carbon film layer 151 (second transition protective film layer 15) is 1 to 20nm, preferably 2 to 10nm. The total thickness of the three amorphous carbon film layers is smaller than that of a conventional single DLC film layer or TA-C film layer, so that the optical composite film layer has high hardness and super wear resistance, and the whole optical composite film layer presents neutral color.

The film thickness of the AF film layer 13 is 5 to 30nm, preferably 10 to 20nm.

In the preparation of the optical composite film layer, the first anti-reflection film layer 11 can be prepared by adopting a multi-arc method (including but not limited to a Filtered Cathode Vacuum Arc (FCVA) method), an electron beam evaporation method, a magnetron sputtering method, a PECVD method and the like. In this embodiment, taking forming a laminated structure composed of a silicon dioxide first low refractive index film layer and a titanium dioxide first high refractive index film layer and a TA-C second amorphous carbon film layer 141 as an example, a magnetron sputtering method is first adopted, corresponding sources of silicon dioxide and titanium dioxide are sequentially turned on, and each of the alternating film layers except for the first top film layer 112 in the third film layer structure is formed under the vacuum degree higher than 2.0E-5 Torr. When the first top layer 112 is formed, magnetron sputtering and filtered cathodic vacuum arc are simultaneously turned on, and the TA-C corresponding source (graphite target) is turned on to dope the TA-C material while forming the silicon dioxide first top layer 112.

After all the film layers in the first anti-reflection film layer 11 are completed, when the second amorphous carbon film layer 141 of the first transition protective film layer 14 is prepared, the magnetron sputtering and the filtered cathode vacuum arc are continuously and synchronously started, and the ionized hydrogen is formed by introducing hydrogen under the vacuum degree higher than 2.0E-5Torr by using a graphite target, wherein the hydrogen flow is 30-70 sccm, and the preferable hydrogen flow is 40-60 sccm. And doped using a source that forms silicon dioxide. And the film forming rate of TA-C is controlled to be lower than 0.02nm/s by the aforementioned method to control the film thickness of the TA-C second amorphous carbon film 141 to be in the range of 1 to 20nm, preferably 2 to 10 nm.

Thereafter, the first amorphous carbon film 121 of the protective film 12 is continuously formed, and the plating method may be multi-arc (including, but not limited to, filtered Cathodic Vacuum Arc (FCVA) method), electron beam evaporation, magnetron sputtering, PECVD, etc. And the ionized gas elements are doped while the first amorphous carbon film layer 121 is formed, so that the first amorphous carbon film layer 121 has a first film layer structure, and the hardness and the wear resistance of the TA-C first amorphous carbon film layer 121 are improved.

In this embodiment, taking the formation of the TA-C first amorphous carbon film layer 121 as an example, by synchronously starting magnetron sputtering and filtering cathode vacuum arc, using a graphite target, and introducing hydrogen gas at a vacuum degree higher than 2.0E-5Torr, the flow rate of the hydrogen gas is 30-70 sccm, preferably 40-60 sccm. And the film formation rate of TA-C can be controlled to be lower than 0.02nm/s by using the function of the conditioning coil disclosed in the invention patent application publication No. CN113903650A, for example, to control the film thickness of the first amorphous carbon film 121 to be in the range of 1 to 20nm, preferably 3 to 10 nm.

Taking the TA-C first amorphous carbon film 121 doped with hydrogen with thickness of 10nm prepared by the above method as an example, the comparison results of expressing the H-doped amount with different hydrogen gas flows are shown in the following table:

As can be seen from the results in the table, at lower hydrogen levels (10 sccm), the TA-C film layer has greater reflectivity and absorptivity, indicating poor overall optical performance. However, when the amount of hydrogen gas was high (90 sccm), there were also significant scratches, indicating deterioration of the friction properties (abrasion resistance). When the hydrogen amount is 30-70 sccm (preferably 40-60 sccm), the reflectivity and absorptivity are lower than 5%, so that the optical performance is better.

After the preparation of the protective film layer 12 (the first amorphous carbon film layer 121) is completed, the second transitional protective film layer 15 is continuously prepared. While forming the second transition protective film layer 15, the magnetron sputtering and the filtered cathode vacuum arc are continuously and synchronously turned on, a graphite target is used, and ionized hydrogen (or a source body for forming a second compound (such as silicon nitride) is simultaneously turned on to perform the doping of the hydrogen and the second compound) is doped while forming the TA-C third amorphous carbon film layer 151 under the vacuum degree higher than 2.0E-5Torr, wherein the ionized hydrogen is formed by introducing hydrogen, the flow rate of the hydrogen is 30-70 sccm, and the film forming rate is controlled to be lower than 0.02nm/s by the foregoing method, so that the film thickness of the third amorphous carbon film layer 151 is controlled to be 1-20 nm, preferably 2-10 nm.

After that, the AF film layer 13 is continuously formed. An AF film layer 13 such as heptadecafluorodecyltrimethoxysilane is continuously prepared on the third amorphous carbon film layer 151 by adopting a thermal resistance evaporation method, a PECVD method and the like, so that a better hydrophobic oleophobic fingerprint-proof effect is given to the optical composite film layer, and the use feeling is improved. The film thickness of the AF film layer 13 is in the range of 5 to 30nm, preferably 10 to 20nm.

So that the total thickness of the finally obtained first transition protective film layer 14, protective film layer 12 and second transition protective film layer 15 is smaller than that of a single DLC film layer or TA-C film layer formed by a conventional method, and the ultra wear resistant optical composite film layer including the first anti-reflection film layer 11 and the AF film layer 13 is made to be neutral in color as a whole.

The second anti-reflection coating layer 16 may be formed by multiple arc methods including, but not limited to, filtered Cathodic Vacuum Arc (FCVA) methods, electron beam evaporation, magnetron sputtering, PECVD, and the like. In this embodiment, taking the forming of a laminated structure composed of a silicon dioxide second low refractive index film layer and a titanium dioxide second high refractive index film layer as an example, a magnetron sputtering method is adopted, corresponding sources of silicon dioxide and titanium dioxide are sequentially turned on, and the silicon dioxide second low refractive index film layer and the titanium dioxide second high refractive index film layer in the second anti-reflection film layer 16 are sequentially and alternately formed under the vacuum degree higher than 2.0E-5 Torr.

Example 1

Taking the preparation of an optical composite film layer as an example in fig. 3, the third film layer structure of the first anti-reflection film layer 11 has a 5-layer structure in which silicon dioxide film layers and titanium dioxide film layers are sequentially alternated, the second amorphous carbon film layer 141, the first amorphous carbon film layer 121 and the third amorphous carbon film layer 151 are doped TA-C film layers, and the AF film layer 13 is a heptadecafluorodecyl trimethoxysilane material, comprising the following steps:

First, the substrate 10 is clamped in the vacuum coating chamber, and one surface (first surface/front surface) of the substrate 10 requiring coating is directed toward the source. The substrate 10 is, for example, a glass substrate 10.

Then, the coating chamber is evacuated, and the surface of the substrate 10 requiring coating is ion-cleaned at a vacuum level higher than 5.0E-5 Torr. The cleaning method comprises etching the glass surface of the substrate 10 by using plasma to activate the coated surface and remove the dirt of particles, thereby increasing the binding force between the substrate 10 and the coating to be coated.

After the ion cleaning is completed, the third film structure of the first anti-reflection film layer 11, the second amorphous carbon film layer 141, the first amorphous carbon film layer 121, the third amorphous carbon film layer 151, and the AF film layer 13 may be sequentially prepared on the front surface of the substrate 10 using the aforementioned method. After all coating steps are completed, vacuum is broken, and the substrate 10 coated with the optical composite film layer is taken out. The structure comprises the following components:

The thickness of each film layer of the third film layer structure from the surface of the substrate 10 is 10nm, 13nm, 24nm, 89nm and 64nm in sequence, and the uppermost silicon dioxide film layer (the first top film layer 112) is doped with a TA-C material.

The TA-C second amorphous carbon film 141 has a thickness of 4nm and is doped with hydrogen and silicon dioxide.

The thickness of the TA-C first amorphous carbon film layer 121 is 2nm, and is doped with hydrogen.

The thickness of the TA-C third amorphous carbon film layer 151 is 10nm, and is doped with hydrogen.

The AF film layer 13 had a thickness of 17nm.

Example 2

Taking the preparation of an optical composite film layer as an example in fig. 4, the third film layer structure of the first anti-reflection film layer 11 has a 5-layer structure in which a silicon dioxide film layer and a titanium dioxide film layer are sequentially alternated, the second amorphous carbon film layer 141, the first amorphous carbon film layer 121 and the third amorphous carbon film layer 151 are doped TA-C film layers, the AF film layer 13 is a heptadecafluorodecyl trimethoxysilane material, and the second anti-reflection film layer 16 has a 5-layer structure in which a silicon dioxide film layer and a titanium dioxide film layer are sequentially alternated. Example 2 differs from example 1 in that after the film plating of the AF film layer 13 is completed: the method also comprises the following steps:

The substrate 10 is taken out, and the substrate 10 is turned over to perform plating on the other surface (second surface/back surface). Firstly vacuumizing, and when the vacuum degree is higher than 5.0E-5Torr, performing ion cleaning on the back surface of the substrate 10, mainly etching the glass surface of the substrate 10 by using plasma to achieve the effects of activating the surface and removing particles and dirt, thereby increasing the bonding force between the substrate 10 and the film layer.

After the ion cleaning is finished, and when the vacuum degree is adjusted to be higher than 2.0E-5Torr, magnetron sputtering is performed, and a silicon dioxide film layer and a titanium dioxide film layer are respectively deposited on the back surface of the substrate 10, so that a second antireflection film layer 16 with a 5-layer structure is formed in turn alternately. At this time, the coating is completed, the vacuum is broken, and the substrate 10 on which the coating is completed is taken out. I.e. the second anti-reflection film 16 is prepared without doping the film. The structure comprises the following components:

The thickness of each film layer of the first anti-reflection film layer 11 from the front surface of the substrate 10 is sequentially 50nm, 13nm, 37nm, 111nm and 69nm, and the silicon dioxide film layer (the first top film layer 112) of the uppermost layer is doped with a TA-C material.

The thickness of the TA-C first amorphous carbon film layer 121 is 10nm, and is doped with hydrogen.

The thickness of the TA-C third amorphous carbon film layer 151 is 2nm, and is doped with hydrogen.

The AF film layer 13 had a thickness of 17nm.

The thickness of each film layer of the second antireflection film layer 16 from the back surface of the substrate 10 is 50nm, 11nm, 38nm, 106nm, 85nm in this order.

Example 2 differs from example 1 in that example 2 is a double-sided film coating, whereas example 1 is a single-sided film coating, and example 2 has a better optical effect than example 1.

Example 3

Also taking the preparation of an optical composite film as an example in fig. 4, the third film structure has a 5-layer structure in which silicon dioxide film and titanium dioxide film alternate in sequence, the second amorphous carbon film 141, the first amorphous carbon film 121 and the third amorphous carbon film 151 are doped TA-C film, the AF film 13 is heptadecafluorodecyl trimethoxysilane material, and the second anti-reflection film 16 has a 5-layer structure in which silicon dioxide film and titanium dioxide film alternate in sequence. The structure comprises the following components:

The thickness of each film layer of the third film layer structure from the front surface of the substrate 10 is sequentially 50nm, 13nm, 37nm, 111nm and 69nm, and the silicon dioxide film layer (the first top film layer 112) of the uppermost layer is doped with a TA-C material.

The thickness of the TA-C first amorphous carbon film layer 121 is 4nm, and is doped with hydrogen.

The thickness of the TA-C third amorphous carbon film layer 151 is 1nm, and is doped with hydrogen.

The AF film layer 13 had a thickness of 17nm.

Example 3 differs from example 2 in that the total thickness of the TA-C amorphous carbon film layer of example 3 is thinner, and the reflectance and absorptivity are better, but the abrasion resistance is also worse than that of example 2.

Comparative example 1

Refer to fig. 7. The AR film layer 22 is common in the market and is prepared by conventional techniques. The substrate 20 is a glass substrate 20, the ar film layer 22 has a 5-layer structure in which silicon oxide film layers (L) and silicon nitride film layers (H) are sequentially alternated, and the AF film layer 21 is a heptadecafluorodecyl trimethoxysilane material. The structure comprises the following components:

The thickness of each of the AR film layers 22 from the front surface of the substrate 20 was 10nm, 700nm, 24nm, 89nm, 64nm in this order. The AF film layer 21 had a thickness of 15nm.

It can be seen that, in the AR film 22 structure, the silicon nitride film located on the second layer 221 needs to have a thickness of 700nm, and the control of the film thickness is limited, so that the optical performance of color neutrality is sacrificed, which results in color development (see the following test results), and affects the visual effect.

Test conditions

Wear resistance: after the optical composite film layer is subjected to steel wool abrasion resistance, the overall abrasion resistance can be obviously improved compared with that of a common AR film.

Test 1: the linear friction, the abrasive was steel wool, loaded at 1kg, and the speed 25 cycles/min (1 cycle back and forth each time). The 8000 linear friction test results showed that the ordinary AR film of comparative example 1 had obvious scratches, whereas the optical composite film of the present utility model had no scratches.

Test 2: the tabletop rubs randomly, the load is 400g, and the speed is 60 cycles/min. The 3000 tabletop random friction test results can show that the ordinary AR film layer of the comparative example 1 has obvious scratches, and the optical composite film layer of the utility model has no scratches.

Spectral properties: the whole film structure of the optical composite film can be adjusted according to the wear resistance requirement of the substrate 10 material, the average reflectivity and the absorption rate are adjustable, the minimum visible light average single-sided reflectivity of a film coating surface can be less than 1%, and the minimum film integral absorption rate can be less than 1%.

And (3) dripping angle test: the dripping angle of the optical composite film layer is more than or equal to 100 degrees, preferably more than or equal to 110 degrees.

Test results:

In summary, the utility model overcomes the defect that the overall appearance color can be influenced and changed under the traditional method of adopting the AR film layer, not only meets the requirement of antireflection, but also obtains better wear resistance, and meanwhile, the whole film layer structure can adjust the average reflectivity and the absorption rate by adjusting the thickness and the doping degree of each film layer according to the wear resistance requirement of the base material, thereby meeting the requirement of diversified hardness requirements.

While embodiments of the present utility model have been described in detail hereinabove, it will be apparent to those skilled in the art that various modifications and variations can be made to these embodiments. It is to be understood that such modifications and variations are within the scope and spirit of the present utility model as set forth in the following claims. Moreover, the utility model described herein is capable of other embodiments and of being practiced or of being carried out in various ways.

Claims

1. An optical composite film, comprising:

2. The optical composite film of claim 1, wherein the first low refractive index film has a refractive index less than the refractive index of the first high refractive index film, the first bottom film closest to the substrate in the first anti-reflection film is the first low refractive index film, and the first top film furthest from the substrate in the first anti-reflection film is the first low refractive index film or the first high refractive index film.

3. The optical composite film according to claim 2, wherein a first transition protective film layer is further provided between the protective film layer and the first anti-reflection film layer, and the first transition protective film layer includes a second amorphous carbon film layer.

4. The optical composite film according to claim 3, wherein the protective film has a first film structure in which additional ionized gas elements are distributed in the first amorphous carbon film, the first transitional protective film has a second film structure in which additional ionized gas elements and a first compound are distributed in the second amorphous carbon film, and the first compound is in contact with the surface of the first top film at the interface of the first transitional protective film and the first antireflection film, and the first compound is the first top film material.

5. The optical composite film according to claim 4, wherein the first anti-reflection film has a third film structure in which the additional second amorphous carbon film material is distributed in the first top film, and the second amorphous carbon film material distributed in the first top film contacts with the surface of the second amorphous carbon film at the interface of the first anti-reflection film and the first transition protective film.

6. The optical composite film according to claim 5, wherein a second transition protective film layer is further provided between the protective film layer and the AF film layer, the second transition protective film layer including a third amorphous carbon film layer.

7. The optical composite film according to claim 6, wherein the second transitional protective film has a fourth film structure in which additional ionized gas elements are distributed in the third amorphous carbon film, or the second transitional protective film has a fourth film structure in which additional ionized gas elements and a second compound are distributed in the third amorphous carbon film, and the second compound is in contact with the surface of the AF film at an interface of the second transitional protective film and the AF film.

8. The optical composite film according to claim 7, wherein the first, second, and third amorphous carbon films comprise DLC films, or the first, second, and third amorphous carbon films comprise TA-C films; the ionized gas elements added in the first amorphous carbon film layer, the ionized gas elements added in the second amorphous carbon film layer and the ionized gas elements added in the third amorphous carbon film layer comprise ionized hydrogen elements.

9. The optical composite film according to claim 1, further comprising: the second antireflection film layer is arranged on a second surface of the substrate opposite to the first surface, the second antireflection film layer comprises alternating layers of second low-refractive-index film layers and second high-refractive-index film layers, the refractive index of the second low-refractive-index film layers is smaller than that of the second high-refractive-index film layers, a second bottom film layer closest to the substrate in the second antireflection film layers is the second low-refractive-index film layer, and a second top film layer farthest from the substrate in the second antireflection film layers is the second low-refractive-index film layer.

10. The optical composite film of claim 9, wherein another implementation of the optical composite film is not provided with at least one of the first and second anti-reflection film layers.