Magnetron sputtering preparation method of antireflection film and antireflection film

Abstract

The invention relates to an antireflection film and a magnetron sputtering preparation method thereof. The method comprises the following steps of: cleaning the surface of a base material by using an ion source; enhancing the binding force of a film layer and the base material; alternately depositing a high-refractive-index material layer and a low-refractive-index material layer; controlling each parameter to enable the thickness to be within a specific range; and the optical performance of the composite film layer is optimized. And finally, ion sources in different modes are used for bombarding the AR plating layer, the density and roughness of the thin film are optimized, the AR plating layer is tamped in a high-power, high-argon-filling and low-oxygen-filling mode, and the surface roughness of the AR plating layer is reduced. The reaction activity of the AR surface layer and the AF is improved through a low-power, low-argon-filling and high-oxygen-filling mode, and the friction resistance of the product is improved. The invention further provides the antireflection film prepared by the method, the antireflection film comprises the substrate and alternately deposited composite film layers, the antireflection film can be applied to base material surfaces of glass with different haze degrees, and the durability of AG glass is greatly improved.

Description

Technical Field

[0001] The present application relates to the field of optical film technology, and in particular to a magnetron sputtering preparation method for an anti-reflection film and an anti-reflection film. Background Art

[0002] With the rapid development of electronic information technology, electronic devices such as mobile phones, computers, and tablets have become essential to our daily lives. During the use of these electronic devices, the display screens serve as the components for information presentation and interaction. The presence of reflections and glare on these displays can affect the user experience. For example, in strong light conditions, reflections and glare can make the screen content difficult to see, causing visual fatigue and even interfering with normal operation.

[0003] To effectively address this issue, AR coating (Anti-Reflective Coating) technology precisely deposits one or more layers of thin film material with specific optical properties onto the surface of optical components, reducing light reflection losses and significantly improving transmittance and optical performance. Its core goal is to reduce light reflection at interfaces, increase the light intensity passing through the optical component, and achieve high-light visibility. By adding an AG etching process to the substrate surface to eliminate surface glare, AG and AR coating technologies are currently widely used in display cover plates and camera lenses for electronic devices such as smartphones and tablets, as well as in solar panels and automotive windshields.

[0004] Although AR coating technology has achieved the above-mentioned results, it still faces many problems that need to be solved in practical applications. Conventional AR film layers perform poorly in terms of wear resistance and corrosion resistance on flat surfaces and AG substrates, and the film layer is easily worn, which not only destroys the integrity of the film layer, but also affects the performance and life of the device. With the continuous iteration and upgrading of electronic products, consumers have put forward higher requirements for the durability of the equipment, and ordinary AR films are obviously difficult to meet market demand. In addition, although conventional super-hard coating technology has improved the hardness of the film layer to a certain extent, the reflectivity is still close to 0.6%, the anti-reflection effect is not ideal, and it is not resistant to friction, and cannot effectively meet the dual requirements of high light transmittance and wear resistance. Therefore, it is necessary to develop an anti-reflection film with excellent wear resistance, corrosion resistance and good anti-reflection effect. Summary of the Invention

[0005] The purpose of this application is to provide a method for preparing an anti-reflection film by magnetron sputtering, the corresponding process control and products of which are stable and reliable, and can achieve a reflectivity of less than 0.2% and a transmittance of more than 95% (visible light range 420-680nm) on the surface of the glass cover after coating. The surface of the glass cover after coating can not only achieve excellent low-reflection and high-transmittance effects. By optimizing the pre-treatment process, the film-base bonding strength is improved and the risk of film shedding is reduced; and by constructing a gradient vacuum cavity structure, the film purity is improved, film formation defects are reduced, and the refractive index and extinction coefficient of high-refractive-index materials are optimized; the hardness and surface activity of the AR film layer are further improved by designing a composite ion source post-treatment process, and the wear resistance of the AR and AF mixed coating is further improved by optimizing the AF film forming process. The purpose of this application is achieved through the following technical solutions. The method for preparing an anti-reflection film by magnetron sputtering includes: Use an ion source to clean the substrate surface; Alternatingly depositing layers of a high refractive index material and layers of a low refractive index material; After forming a composite film layer of a high refractive index material layer and a low refractive index material layer, bombarding the surface of the composite film layer using an ion source; Wherein, the high refractive index material layer is niobium oxide, tantalum oxide, zirconium oxide, titanium oxide, silicon nitride or aluminum oxide, and the low refractive index material layer is silicon oxynitride, aluminum silicon oxynitride or silicon dioxide; The surface of the composite film layer is bombarded using ion sources with first and second process parameters respectively, wherein the power and inert gas ratio in the first process parameter are higher than the power and inert gas ratio in the second process parameter, and the oxygen ratio in the first process parameter is lower than the oxygen ratio in the second process parameter.

[0006] In one embodiment, the cleaning time is in the range of 100s-360s, the ion beam acceleration voltage of the ion source is in the range of 500V-1600V, the ion beam current is in the range of 1mA-150mA, and the distance between the substrate and the ion source is in the range of 10mm-50mm.

[0007] In one embodiment, when sputtering to form a high refractive index material layer, the vacuum degree is controlled at 2E -3 Pa-2E -1 Pa range, the operating cycle is in the range of 100s to 500s, the sputtering power is controlled in the range of 3kw-18kw, the argon filling amount is controlled in the range of 100sccm-600sccm, the nitrogen filling amount is controlled in the range of 10sccm-80sccm, and the coating rate is controlled in the range of 0.2nm / s-0.6nm / s.

[0008] In one embodiment, when sputtering to form the low refractive index material layer, the vacuum degree is controlled at 2E -3 Pa-2E-1 In the range of Pa, the operation tempo is in the range of 100s to 500s, the sputtering power is controlled in the range of 4kw-18kw, the argon filling amount is controlled in the range of 100sccm-600sccm, the oxygen filling amount is controlled in the range of 100sccm-600sccm, and the film plating rate is controlled in the range of 0.2nm / s-0.6nm / s.

[0009] In one embodiment, the ion source bombards the surface of the composite film layer, and further includes a step of spraying to form the AF film layer.

[0010] In one embodiment, two or more anode ion sources are used to bombard the surface of the film layer.

[0011] In one embodiment, during the process of alternately forming the high refractive index material layer and the low refractive index material layer, the surface of each high refractive index material layer is bombarded by an ion source.

[0012] In one embodiment, the bombardment time of each high refractive index layer decreases first and then increases in the direction of the substrate towards the composite film layer.

[0013] In one embodiment, a gradient heating method is used to increase the temperature during the drying process of spraying to form the AF film.

[0014] The application further provides a kind of antireflection film, which is prepared by the antireflection film magnetron sputtering preparation method described above, comprising: a substrate; a composite film layer formed on the surface of the substrate, the composite film layer includes alternately deposited high refractive index material layers and low refractive index material layers, wherein the high refractive index material layer is niobium oxide, tantalum oxide, zirconium oxide, titanium oxide, silicon nitride or aluminum oxide, and the low refractive index material layer is silicon oxynitride, aluminum silicon oxynitride or silicon dioxide.

[0015] Compared with the prior art, the application has the following beneficial effects: The magnetron sputtering method for preparing an anti-reflection film disclosed herein alternately deposits layers of a high-refractive-index material (niobium oxide, tantalum oxide, zirconium oxide, titanium oxide, silicon nitride, or aluminum oxide) and layers of a low-refractive-index material (silicon oxynitride, aluminum silicon oxynitride, or silicon dioxide). The thickness of each layer is controlled (the high-refractive-index layer is controlled within a range of 5nm to 400nm, and the low-refractive-index layer is controlled within a range of 5nm to 600nm). This method forms an optimized optical film structure, effectively reducing light reflection from the glass cover surface and improving optical performance. By controlling process parameters at each step, such as the ion source cleaning time, ion beam acceleration voltage, ion beam current, substrate-to-source spacing, and vacuum level, sputtering power, gas volume, coating rate, and AF annealing temperature and time during sputtering to form the high-refractive-index and low-refractive-index layers, the stability and consistency of the preparation process are ensured, resulting in stable performance of the resulting anti-reflection film product.

[0016] This application can achieve a surface reflectivity of less than 0.2% and a transmittance of greater than 95% (visible light range 420-680nm) for the coated glass cover. By optimizing the post-processing parameters of the ion source of the optical film layer, this application improves the surface roughness of the AR. By regulating the deposition vacuum level of the high-refractive index material layer, the introduction of impurity gases during the deposition of the upper layer during the film formation process is reduced, film defects are avoided, and the purity of the film layer is improved, thereby regulating the refractive index and extinction coefficient of the high-refractive index material. At the same time, reasonable control of the sputtering parameters of each layer, such as vacuum level, sputtering power, and gas volume, helps to form a film layer with a stable structure, increased hardness, and low roughness. This avoids the undesirable problems of poor wear resistance, weak corrosion resistance, and easy wear of the film layer under conventional coating parameters, thereby improving the durability and service life of the anti-reflection film.

[0017] After forming a composite film layer of a high refractive index material layer and a low refractive index material layer, the surface of the composite film layer is bombarded using an anode ion source with different processing modes to reduce the roughness of the film layer and improve the density and hardness of the film layer.

[0018] The anti-reflection film of the present application comprises a substrate and a composite film layer formed on the substrate surface. The composite film layer is composed of alternating layers of high-refractive-index material and low-refractive-index material. This anti-reflection film inherits all the benefits of the above-mentioned preparation method, with excellent optical properties and hardness, as well as low roughness. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] Figure 1 This is a schematic flow chart of the magnetron sputtering method for preparing an anti-reflection film according to the present invention; Figure 2 It is a schematic structural diagram of the anti-reflection film of the present application; Figure 3 is the reflectivity of the anti-reflection film of this application.

[0020] Explanation of reference numerals: 100, substrate; 200, composite film layer; 210, high refractive index material layer; 220, low refractive index material layer. DETAILED DESCRIPTION

[0021] In order to make the above-mentioned objects, features and advantages of the present application more obvious and easy to understand, the specific implementation methods of the present application are described in detail below in conjunction with the accompanying drawings. It will be understood that the specific embodiments described herein are only used to explain the present application, rather than to limit the present application. It should also be noted that, for ease of description, only some, rather than all, structures related to the present application are shown in the accompanying drawings. Based on the embodiments in the present application, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of this application.

[0022] As used herein, the terms "comprise," "comprising," and "having," and any variations thereof, are intended to cover non-exclusive inclusions. For example, a process, method, system, product, or apparatus comprising a series of steps or elements is not limited to the listed steps or elements but may optionally include steps or elements not listed, or may optionally include other steps or elements inherent to the process, method, product, or apparatus.

[0023] References herein to "embodiments" mean that a particular feature, structure, or characteristic described in connection with the embodiments may be included in at least one embodiment of the present application. The appearance of this phrase in various places in the specification does not necessarily refer to the same embodiment, nor does it constitute an independent or alternative embodiment that is mutually exclusive of other embodiments. It is understood, both explicitly and implicitly, by those skilled in the art that the embodiments described herein may be combined with other embodiments.

[0024] During actual use, reflections and glare on displays can reduce visual clarity and comfort, and may also affect device accuracy. To effectively address this issue, AR coating (Anti-Reflective Coating) technology has emerged. By depositing multiple layers of thin film materials with specialized optical properties on the surface of optical components, AR coating reduces light reflection loss, improves transmittance and optical performance, and thus reduces light reflection at interfaces, increasing the light intensity passing through the optical component and achieving excellent high-light visibility. Conventional AR coatings lack wear and corrosion resistance and are prone to wear, which not only damages the integrity of the coating but also seriously affects the performance and lifespan of the device. With the continuous upgrading of electronic products, consumers have higher demands for device durability, and conventional AR coatings are no longer able to meet market demands. Furthermore, while conventional super-hard coating technology improves the hardness of the coating, its reflectivity remains close to 0.6%, resulting in suboptimal anti-reflection performance and poor abrasion resistance.

[0025] In this context, the present application provides a method for preparing an anti-reflection film by magnetron sputtering. As an advanced thin film preparation technology, magnetron sputtering technology has the advantages of high deposition rate, good film quality, and strong process controllability, providing strong technical support for the preparation of high-performance anti-reflection films. The present application aims to optimize the magnetron sputtering preparation process, control various process parameters, and effectively regulate the optical properties of the anti-reflection film and the purity, hardness, optical refractive index and roughness of the film layer, thereby preparing an anti-reflection film with low reflectivity, high transmittance and excellent wear resistance to meet the market demand for high-performance anti-reflection films. Next, the anti-reflection film preparation method by magnetron sputtering of the present application and the specific technical solution of the anti-reflection film will be introduced in detail. Please refer to Figure 1 In a preferred embodiment of the present application, a method for preparing an anti-reflection film by magnetron sputtering includes: Use an ion source to clean the substrate surface; Alternately depositing high refractive index material layers 210 and low refractive index material layers 220; After forming the composite film layer 200 of the high refractive index material layer 210 and the low refractive index material layer 220, an ion source is used to bombard the surface of the composite film layer 200; The high refractive index material layer 210 is niobium oxide, silicon nitride or aluminum oxide, and the low refractive index material layer 220 is silicon oxynitride, aluminum silicon oxynitride or silicon dioxide.

[0026] First, the ion source is turned on and various parameters, such as the ion beam acceleration voltage and ion beam current, are adjusted to ensure an appropriate working state. The ion source is then used to perform a comprehensive and detailed cleaning of the substrate surface. During the cleaning process, the cleaning time is controlled within the range of 100s-360s, and the distance between the substrate and the ion source is reasonably set within the range of 10mm-50mm. This ensures that the ion beam can act evenly and effectively on the substrate surface, providing a smooth and highly active base surface for the subsequent coating process, thereby enhancing the bonding strength between the film layer and the substrate.

[0027] Then, the alternating deposition phase begins. The vacuum is controlled at 2E -3 Pa-2E -1 In a sputtering environment within the range of Pa, the high refractive index material layer 210 is first deposited. Niobium oxide, tantalum oxide, zirconium oxide, silicon nitride or aluminum oxide are selected as high refractive index materials. By controlling the sputtering power within the range of 3kw-18kw, the argon filling amount within the range of 100sccm-400sccm, the nitrogen filling amount within the range of 10sccm-80sccm and the coating rate within the range of 0.1nm / s-0.6nm / s and other parameters, the thickness of the high refractive index material layer 210 is controlled within the range of 5nm-400nm. A high and low vacuum system is constructed before and after the deposition of the high refractive index material, in which the film forming chamber adopts low vacuum, and the vacuum degree range is 2E -2 Pa to 2E -1 Pa; The high vacuum chamber is used as a buffer chamber to absorb the impurity gas of the upper film forming layer and reduce the impurity gas that escapes from the vacuum into the film forming chamber, so as to achieve the purpose of high-quality film formation.

[0028] After the deposition of a high refractive index material layer 210 is completed, the deposition of the low refractive index material layer 220 is switched. Silicon oxynitride, aluminum silicon oxynitride or silicon dioxide is used as the low refractive index material, and the vacuum degree is controlled at 2E -3 Pa-2E -1 Within the Pa range, the operating cycle is 100s to 500s, the sputtering power is controlled in the range of 4kw-18kw, the argon filling amount is controlled in the range of 100sccm-600sccm, the oxygen filling amount is controlled in the range of 100sccm-600sccm, and the coating rate is controlled in the range of 0.2nm / s-0.6nm / s.

[0029] By repeating the alternating deposition in this manner, a composite film layer 200 having a specific structure of a high refractive index material layer 210 and a low refractive index material layer 220 is gradually constructed.

[0030] After the composite film 200, consisting of a complete high-refractive-index material layer 210 and a low-refractive-index material layer 220, is formed, the ion source is activated again to perform deep bombardment on the surface of the composite film 200. This bombardment duration is strictly set to greater than 500 seconds, and ion source parameters such as ion beam energy and gas filling can be further adjusted during the bombardment process based on actual needs and process optimization to ensure that the ion beam can fully act on the surface of the composite film 200, further densifying and strengthening the film.

[0031] By controlling ion source parameters as well as cleaning time and spacing, contaminants such as impurities, dust, and oxide layers can be removed from the substrate surface. Effective cleaning provides a clean, flat substrate for subsequent film deposition, strengthening the bond between the film and the substrate, and improving the stability and reliability of the anti-reflection film. During the ion source cleaning process, the interaction between the ion beam and the substrate surface can energize the atoms on the substrate surface, generating a certain level of activity. This facilitates better bonding between the atoms in the subsequently deposited film layer and the substrate surface, further improving the quality and performance of the film.

[0032] By separately controlling various parameters during the deposition process of the high-refractive-index material layer 210 and the low-refractive-index material layer 220, such as sputtering power, gas volume, and coating rate, the thickness of the high-refractive-index material layer 210 can be stably controlled within the range of 5nm-400nm, and the thickness of the low-refractive-index material layer 220 can be stably controlled within the range of 5nm-600nm. The combination of film layers of different thicknesses can produce a specific optical interference effect, thereby effectively adjusting the reflection and transmission characteristics of light to achieve the goals of low reflectivity and high transmittance.

[0033] Niobium oxide, tantalum oxide, zirconium oxide, titanium oxide, silicon nitride or aluminum oxide is selected as the high refractive index material, and silicon oxynitride, aluminum silicon oxynitride or silicon dioxide is selected as the low refractive index material. These materials have excellent optical properties, chemical stability and mechanical properties. The reasonable combination and alternating deposition of high refractive index materials and low refractive index materials can form a stacked film system with a specific optical structure, optimize the optical properties of the anti-reflection film, and at the same time improve the wear resistance and corrosion resistance of the film layer, thereby extending the service life of the anti-reflection film.

[0034] The two modes of ion source bombardment enable the ion beam to fully act on the surface of the composite film layer 200, further squeezing and arranging the atoms in the film layer, making the film surface denser and less rough. The dense film structure can also effectively resist external friction and scratches, reducing wear and damage to the film layer, thereby ensuring the performance stability of the anti-reflection film during long-term use. In addition, during the ion source bombardment process, the surface silica coating can be activated, enhancing the bonding strength of the AF coating and the AR coating, thereby further improving the wear resistance of the composite coating.

[0035] Specifically, the surface of the composite film layer is bombarded using ion sources with first and second process parameters, respectively. The power and inert gas ratio in the first process parameter is higher than the power and inert gas in the second process parameter, and the oxygen ratio in the first process parameter is smaller than the oxygen ratio in the second process parameter, that is, the high power, high argon filling, low oxygen filling mode and the low power, low argon filling, high oxygen filling mode, respectively. The high power, high argon filling, low oxygen filling mode is used to compact the AR coating and reduce the surface roughness of the AR coating; while the low power, low argon filling, high oxygen filling mode is used to increase the reaction activity of the AR surface layer and AF, and improve the friction resistance of the product.

[0036] The cleaning time is within the range of 100s-360s, the ion beam acceleration voltage of the ion source is within the range of 500V-1200V, the ion beam current is within the range of 1mA-150mA, and the distance between the substrate and the ion source is within the range of 10mm-50mm. The cleaning time, ion beam acceleration voltage, ion beam current, and the distance between the substrate and the ion source work synergistically to avoid damage to the substrate surface caused by excessive cleaning. While ensuring the removal of contaminants, by controlling the ion beam acceleration voltage and ion beam current, we prevent excessive ion energy or an overly dense ion beam from causing adverse effects such as etching and roughening on the substrate surface.

[0037] When the high refractive index material layer 210 is formed by sputtering, the vacuum degree is controlled at 2E -2 Pa-2E -1 Pa range, the operating cycle is between 100s and 500s, the sputtering power is controlled in the range of 3kw-18kw, the argon filling amount is controlled in the range of 100sccm-400sccm, the nitrogen filling amount is controlled in the range of 30sccm-50sccm, and the coating rate is controlled in the range of 0.1nm / s-0.6nm / s.

[0038] The vacuum degree of the low vacuum buffer chamber is 2E -3 Pa-2E -2 Pa, used to reduce gas crosstalk in the film forming chamber.

[0039] When the low refractive index material layer 220 is formed by sputtering, the vacuum degree is controlled at 2E -3 Pa-2E -1 Within the Pa range, the sputtering power is controlled in the range of 4kw-18kw, the argon filling amount is controlled in the range of 100sccm-600sccm, the oxygen filling amount is controlled in the range of 100sccm-600sccm, and the coating rate is controlled in the range of 0.2nm / s-0.6nm / s.

[0040] In the magnetron sputtering preparation process of the anti-reflection film, in addition to the steps described above, a cleaning step and an inspection link are also set.

[0041] The cleaning step is an important pre-process to ensure the quality of the substrate 100 and improve the performance of the anti-reflection film. Place the substrate 100 in a dedicated cleaning tank and select a suitable cleaning agent based on the material of the substrate 100 and the degree of surface contamination. For common metal substrates 100, neutral or weakly alkaline chemical cleaning agents can be used. Such cleaning agents can effectively remove pollutants such as oil, dust and part of the oxide layer on the surface of the substrate 100 without causing corrosion damage to the substrate 100. After diluting the cleaning agent in a certain proportion, inject it into the cleaning tank so that the substrate 100 is completely immersed in it. Subsequently, start the ultrasonic cleaning equipment and use the cavitation effect generated by ultrasonic waves in the liquid to completely remove stubborn pollutants.

[0042] After ultrasonic cleaning is completed, the substrate 100 is taken out of the cleaning tank and rinsed with deionized water several times. During the rinsing process, spraying or soaking can be used to ensure that the deionized water can fully cover the surface of the substrate 100, and the number of rinses is not less than 3 times to ensure the cleanliness of the surface of the substrate 100. After rinsing, the substrate 100 is dried. The substrate 100 is placed in a clean drying oven, and the temperature in the drying oven is controlled at 60℃-80℃. This temperature range can quickly evaporate the moisture on the surface of the substrate 100, and will not cause deformation or performance changes of the substrate 100 due to excessive temperature. The drying time depends on the size and thickness of the substrate 100, generally 30-60 minutes, to ensure that the surface of the substrate 100 is completely dry without any moisture residue.

[0043] After completing the cleaning and drying steps, the inspection phase begins. Professional testing equipment is used to conduct a comprehensive inspection of the substrate 100, including appearance inspection and performance inspection. The appearance inspection mainly uses a high-power microscope or optical inspection instrument to observe whether there are defects such as scratches, cracks, stains, etc. on the surface of the substrate 100 to ensure that the surface of the substrate 100 is flat, smooth, and undamaged. The performance inspection measures key parameters such as the thickness, flatness, and roughness of the substrate 100 according to the requirements for the preparation of the anti-reflection film. For example, a profilometer is used to measure the surface roughness of the substrate 100, and its value is required to be controlled within a certain range to ensure that the film layer can be evenly deposited during subsequent coating. At the same time, the thickness of the substrate 100 is tested to ensure that it meets the design requirements to avoid affecting the optical performance of the anti-reflection film due to the uneven thickness of the substrate 100.

[0044] In the preparation process of the anti-reflective film by magnetron sputtering, in order to further improve the performance of the film, the vacuum degree of the film coating chamber and the buffer chamber needs to be optimized. Specifically, the vacuum degree of the film coating chamber is low, and the vacuum degree of the buffer chamber is high. The impurity gas generated during film formation will escape to the buffer chamber, avoiding the participation of impurity gas in the next film formation process. High-energy particles are beneficial to improve the energy of sputtering particles and improve the film density. The running cycle is selected according to the material, structure and expected performance index of the film. Different types of ion sources or different working parameters of the same type of ion source are selected, such as ion beam acceleration voltage, ion beam current, ion species, etc. Different types of anode ion sources or different parameter settings have different energy and penetration ability of the ion beam. Bombarding the film surface with two or more anode ion sources can affect the film from multiple angles and energy levels. The bombardment of the first ion source can initially compact the atoms on the surface of the film, reducing the pores and defects in the film. The second ion source can further penetrate the interior of the film, allowing the film atoms to be more closely arranged and forming a more dense structure. Bombarding each anode ion source will have a unique effect on the microstructure of the film. By using two or more ion sources for bombardment, the advantages of each can be used to control the grain size, orientation and distribution of the film.

[0045] In the preparation process of the anti-reflective film, the high refractive index material layer 210 and the low refractive index material layer 220 are alternately formed. Specifically, in the process of sequentially depositing the high refractive index material layer 210 and the low refractive index material layer 220 by magnetron sputtering, the refractive index of the high refractive index material layer 210 is optimized by optimizing the deposition environment of the high refractive index material for each layer of the high refractive index material layer 210 just deposited. The difference between the high refractive index material and the low refractive index material is enlarged, further improving the optical performance of the overall film.

[0046] During the deposition of the high refractive index material layer 210, there may be some loose structures, adsorbed impurity gas molecules and incompletely combined atoms on its surface. By constructing a high-low vacuum system, the introduction of stray gas during film formation is reduced, the defects of the 210 material layer are reduced, and the optical performance is improved.

[0047] As the composite film 200 is built upwards, the high refractive index material layer 210 enters the middle layer. At this time, the bombardment time of the ion source is gradually reduced, and for the high refractive index material layer 210 of the middle layer, the bombardment time is shortened to 150s-250s. This is because the middle layer mainly plays a role in adjusting the optical performance and transition in the composite film 200, and too long bombardment time may cause unnecessary damage to the relatively stable structure that has been formed. Moreover, the combination of the middle layer and the adjacent layer is relatively easy to control, and appropriately shortening the bombardment time can improve the preparation efficiency while ensuring the performance.

[0048] When the post-treatment is performed on the surface of the composite film layer 200, the composite film layer surface is treated by using mixed gas with different energy and different components. The surface of the film layer is first consolidated by using a treatment process of high-power, high-argon and low-oxygen mixed gas, and then the connection layer of AR and AF is activated by injecting high-oxygen and low-argon mixed gas to enhance the binding force of AR and AF. The post-treatment process of high-power, high-argon and low-oxygen first helps to form a dense and low-roughness micro-surface in the composite film layer 200, thereby enhancing the resistance of the surface layer to the external environment, ensuring the performance stability of the antireflection film in the long-term use process, and improving the overall performance of the antireflection film.

[0049] After the ion bombardment treatment process of the composite layer 200 is completed, the AF spraying treatment is performed. In order to ensure the overall performance of the AF, gradient temperature baking treatment and standing treatment are required after the AF is sprayed on the composite film layer. The baking process adopts a gradient temperature rising mode, first uses low temperature to solidify the AF coating morphology, and then uses high temperature to remove the solvent, which is beneficial to form an AF coating with high uniformity and low defects. Then standing is performed to ensure that the AF connection layer and the AF reaction are fully static. The standing time is generally between 0.5h and 5h.

[0050] In order to ensure that the AF coating is not damaged during the cleaning process, a neutral detergent cleaning process is then used. Specifically, first, according to the material characteristics of the film layer and the types of impurities that may be left in the previous process, select the appropriate neutral detergent. Pour the prepared neutral detergent into a dedicated flat plate cleaning machine, control the temperature of the detergent between 25℃-55℃. Slowly put the sample with the composite film layer into the cleaning machine, control the PH value in the cleaning process between 6 to 8. The cleaning time is generally between 5min-30min.

[0051] The application further provides an antireflection film prepared by using the antireflection film magnetron sputtering preparation method. A substrate 100; A composite film layer 200 is formed on the surface of the substrate 100, and the composite film layer 200 includes alternating layers of high refractive index material layers 210 and low refractive index material layers 220, wherein the high refractive index material layer 210 is niobium oxide, silicon nitride or aluminum oxide, and the low refractive index material layer 220 is silicon oxynitride, aluminum silicon oxynitride or silicon dioxide.

[0052] Referring to Figure 3 The formed antireflection film has a reflectivity of less than 0.2% in the wavelength range of 400nm-700nm. Specific embodiments Some specific embodiments will be further introduced below to further explain the technical solutions of the application.

[0054] Example 1 A continuous magnetron sputtering method for a wear-resistant, long-life AR film is completed by the following steps: 1) Substrate cleaning: The substrate is cleaned by flat plate or ultrasonic cleaning. Alkaline detergent is used for flat plate cleaning. Three detergent tanks and four pure water tanks are set up. After cleaning, the substrate is dried by hot air. 2) Cleaning: The dried substrate obtained in step 1) is attached to the coated substrate and cleaned by an ion source. The cleaning time is between 100s and 360s. The ion beam acceleration voltage of the ion source is U = 500V, the ion beam current is I = 150mA, and the distance between the substrate and the ion source is 50mm. 3) Coating: High and low refractive index materials are evenly stacked and coated on the clean substrate surface. After the AR coating is completed, the excitation source is used to bombard the film surface to increase the density of the film.

[0055] 4) Parameter inspection: spot check the optical spectrum and film firmness of the products off the machine; 5) Re-cleaning: The coated substrate is cleaned again. A neutral detergent is used for this process. After cleaning, the substrate is dried in a hot air dryer. 6) Appearance inspection: Check the appearance of the substrate after coating to complete the product production.

[0056] The vacuum degree of the high refractive index material layer in step 3) is 2.5E during coating -2 Pa, the sputtering power of the niobium oxide target was controlled at 7 kW, the argon filling amount was controlled at 300 sccm, the oxygen filling amount was controlled at 30 sccm, and the coating rate was controlled at 0.4 nm / s.

[0057] The vacuum degree of the low refractive index material layer in step 3) is 2.5E during coating -2 Pa, SiO2 sputtering power is controlled at 6 kW, argon filling amount is controlled at 350 sccm, oxygen filling amount is controlled at 130 sccm, and coating rate is controlled at 0.2 nm / s.

[0058] The resulting abrasion-resistant, long-life AR film achieves a hardness of up to 9H pencil hardness, a roughness range of 0.07μm to 0.078, a high-refractive index of 2.25 to 2.39, and a reflectivity of less than 0.2. Abrasion resistance: Under conditions of 25°C / 65% RH, a Samsung eraser was used to rub the sample surface back and forth at a speed of 40 cycles / min and a stroke of approximately 40mm. After 4,000 cycles, the water drop angle remained greater than 100°. Rubbing with alcohol was also demonstrated to be effective over 10,000 times.

[0059] Example 2 It includes a substrate and a composite film layer arranged on the surface of the substrate. When the substrate is AG glass, the contact area between the AG particles on the surface of the AG glass and the rubber block is smaller. The higher the AG haze, the worse the wear resistance. The AG glass used in this application has a transmittance haze between 5 and 50.

[0060] 1) Substrate cleaning: The substrate is cleaned by flat plate or ultrasonic cleaning. Alkaline detergent is used for flat plate cleaning. Three detergent tanks and four pure water tanks are set up. After cleaning, the substrate is dried by hot air. 2) Cleaning: The dried substrate obtained in step 1) is attached to the coated substrate and cleaned by the anode ion source. The cleaning time is between 100s and 360s. The ion beam acceleration voltage of the anode ion source is U = 1200V, the ion beam current is I = 100mA, and the distance between the substrate and the anode ion source is 10mm. 3) Coating: High and low refractive index materials are evenly stacked and coated on a clean substrate surface. After the AR coating is completed, the film surface is bombarded using an anodic ion source. Four consecutive anodic ion sources are used to bombard the film surface. The bombardment time is increased from about 50s to 200s for ordinary glass products to about 500s to 1000s, which can effectively reduce the roughness of the film layer and significantly improve the friction performance.

[0061] 4) Parameter inspection: spot check the optical spectrum and film firmness of the products off the machine; 5) Re-cleaning: The coated substrate is cleaned again. A neutral detergent is used for this process. After cleaning, the substrate is dried in a hot air dryer. 6) Appearance inspection: Check the appearance of the substrate after coating to complete the product production.

[0062] The vacuum degree of the high refractive index material layer in step 3) is 2.5E during coating -2 Pa, the sputtering power of the niobium oxide target was controlled at 18 kW, the argon filling amount was controlled at 400 sccm, the oxygen filling amount was controlled at 50 sccm, and the coating rate was controlled at 0.6 nm / s.

[0063] The vacuum degree of the low refractive index material layer in step 3) is 0.5E during coating -2 Pa, SiO2 sputtering power is controlled at 16 kW, argon filling amount is controlled at 500 sccm, oxygen filling amount is controlled at 250 sccm, and coating rate is controlled at 0.4 nm / s.

[0064] In step 3), when the first two anode ion sources bombard the membrane surface, the power is controlled at 20 kW, the argon filling amount is controlled at 500 sccm, and the oxygen filling amount is controlled at 0 sccm. When the second two anode ion sources bombard the membrane surface, the power is controlled at 10 kW, the argon filling amount is controlled at 300 sccm, and the oxygen filling amount is controlled at 200 sccm.

[0065] Example 3 This application deeply optimizes the AR coating mentioned above. When the high-refractive-index coating material is silicon nitride and the low-refractive-index material is silicon dioxide, the gases in the silicon nitride and silicon dioxide films will crosstalk during film formation, affecting the refractive index of the materials. Furthermore, the quality of the AF film formation is also related to the improvement of wear resistance.

[0066] 1) Substrate cleaning: The substrate is cleaned by flat plate or ultrasonic cleaning. Alkaline detergent is used for flat plate cleaning. Three detergent tanks and four pure water tanks are set up. After cleaning, the substrate is dried by hot air. 2) Cleaning: The dried substrate obtained in step 1) is attached to the coated substrate and cleaned by the anode ion source. The cleaning time is between 100s and 360s. The ion beam acceleration voltage of the anode ion source is U = 1200V, the ion beam current is I = 100mA, and the distance between the substrate and the anode ion source is 10mm. 3) The high vacuum value of the buffer chamber is set to 2.5E -3 Pa; 4) Coating: High and low refractive index materials are evenly stacked and coated on a clean substrate surface. After the AR coating is completed, the film surface is bombarded using an anodic ion source. Four consecutive anodic ion sources are used to bombard the film surface. The bombardment time is increased from about 50s to 200s for ordinary glass products to about 500s to 1000s, which can effectively reduce the roughness of the film layer and significantly improve the friction performance.

[0067] 5) Parameter inspection: spot check the optical spectrum and film firmness of the products off the machine; 6) Spray AF: Construct a temperature gradient during baking, optimize the AF film quality, and further improve the friction resistance of the composite film layer by extending the growth time to 6 hours.

[0068] 7) Re-cleaning: The coated substrate is cleaned again. A neutral detergent is used for cleaning the substrate. After cleaning, the sample is dried in a hot air dryer. 8) Appearance inspection: Check the appearance of the substrate after coating to complete the product production.

[0069] The vacuum degree of the high refractive index material layer in step 4) is 2.5E during coating -1Pa, the silicon nitride target sputtering power is controlled at 18 kW, the argon filling amount is controlled at 400 sccm, the nitrogen filling amount is controlled at 180 sccm, the coating rate is controlled at 0.6 nm / s, and the material refractive index is controlled between 1.97 and 2.03, which greatly alleviates the cross-gas problem of continuous coating equipment.

[0070] The vacuum degree of the low refractive index material layer in step 4) is 0.5E during coating -1 Pa, SiO2 sputtering power is controlled at 16 kW, argon filling amount is controlled at 500 sccm, oxygen filling amount is controlled at 250 sccm, and coating rate is controlled at 0.4 nm / s.

[0071] After the composite film was formed, the film surface was bombarded with an anodic ion source using the two parameter settings described in Case 2 to test its final abrasion resistance. Under a 25°C / 65% RH environment, with a substrate haze of 0.07, a Samsung eraser was applied with a 1kg load and rubbed back and forth across the sample surface at a speed of 40 cycles / min and a stroke of approximately 40mm. After 6,000 cycles, the water drop angle was >100°. Rubbing with alcohol increased the test to over 100,000 cycles.

[0072] As can be seen from the foregoing, this application proposes an anti-reflection film and a magnetron sputtering method for preparing the same. In the preparation method, the substrate is first cleaned and inspected, and a suitable cleaning agent is selected. After ultrasonic cleaning, deionized water rinsing, and drying, the substrate surface is then cleaned. The ion source parameters are activated and adjusted, with the cleaning time controlled to between 100 seconds and 360 seconds, and the distance between the substrate and the ion source to between 10 mm and 50 mm. Impurities, dust, and oxide layers on the substrate surface are removed, the bonding between the film layer and the substrate is enhanced, and the atoms on the substrate surface are activated.

[0073] Subsequently, layers of high and low refractive index materials are alternately deposited. Under vacuum conditions, by controlling parameters such as sputtering power, gas volume, and coating rate, the thickness of the high refractive index material layer is controlled between 5nm and 400nm, and the thickness of the low refractive index material layer is controlled between 5nm and 600nm. The combination of layers of varying thickness creates an optical interference effect, achieving low reflectivity and high transmittance.

[0074] After the complete composite film is formed, the ion source is reactivated for deep bombardment, with high power, high argon, low oxygen mode for 300 seconds and low power, low argon, high oxygen mode for 300 seconds. Parameters are adjusted as needed to densify and activate the film, reduce roughness, improve wear resistance, and enhance the bond between the AR connecting layer and the AF film. Final abrasion resistance: Under a 25°C / 65% RH environment, with a substrate haze of 45, a Samsung eraser was applied with a 1kg load, rubbed back and forth across the sample surface at a speed of 40 cycles / min and a stroke of approximately 40mm. After 5,000 cycles, the water drop angle was >100°. Rubbing with alcohol was also possible for over 50,000 cycles.

[0075] This application also provides an anti-reflection film, prepared by the above method, comprising a substrate and a composite film layer formed on the substrate's surface, the composite film layer being composed of alternating layers of high-refractive-index material and low-refractive-index material. This method optimizes the optical, mechanical, and stability properties of the anti-reflection film through precise control of multiple steps, thereby extending its service life.

[0076] The above is only a specific implementation of the present application. Any other improvements made based on the concept of the present application are considered to be within the scope of protection of the present application.

Claims

1. A method for preparing an anti-reflection film by magnetron sputtering, characterized in that: include: Use an ion source to clean the substrate surface; Alternatingly depositing layers of a high refractive index material and layers of a low refractive index material; After forming a composite film layer of a high refractive index material layer and a low refractive index material layer, bombarding the surface of the composite film layer using an ion source; Wherein, the high refractive index material layer is niobium oxide, tantalum oxide, zirconium oxide, titanium oxide, silicon nitride or aluminum oxide, and the low refractive index material layer is silicon oxynitride, aluminum silicon oxynitride or silicon dioxide; The surface of the composite film layer is bombarded using ion sources with first and second process parameters respectively, wherein the power and inert gas ratio in the first process parameter are higher than the power and inert gas ratio in the second process parameter, and the oxygen ratio in the first process parameter is lower than the oxygen ratio in the second process parameter.

2. The method for preparing an anti-reflection film by magnetron sputtering according to claim 1, wherein: The cleaning time is within the range of 100s-360s, the ion beam acceleration voltage of the ion source is within the range of 500V-1600V, the ion beam current is within the range of 1mA-150mA, and the distance between the substrate and the ion source is within the range of 10mm-50mm.

3. The method for preparing an anti-reflection film by magnetron sputtering according to claim 1, wherein: When sputtering to form a high refractive index material layer, the vacuum degree is controlled at 2E -3 Pa-2E -1 Within the Pa range, the sputtering power is controlled within the range of 3kw-18kw, the argon filling amount is controlled within the range of 100sccm-600sccm, the nitrogen filling amount is controlled within the range of 10sccm-80sccm, and the coating rate is controlled within the range of 0.2nm / s-0.6nm / s.

4. The method for preparing an anti-reflection film by magnetron sputtering according to claim 3, wherein: When sputtering to form a low refractive index material layer, the vacuum degree is controlled at 2E -3 Pa-2E -1 Within the Pa range, the sputtering power is controlled within the range of 4kw-18kw, the argon filling amount is controlled within the range of 100sccm-600sccm, the oxygen filling amount is controlled within the range of 100sccm-600sccm, and the coating rate is controlled within the range of 0.2nm / s-0.6nm / s.

5. The method for preparing an anti-reflection film by magnetron sputtering according to claim 1, wherein: After the ion source bombards the surface of the composite film layer, the process also includes a step of spraying to form an AF film layer.

6. The method for preparing an anti-reflection film by magnetron sputtering according to claim 1, wherein: Two or more anode ion sources are used to bombard the membrane surface.

7. The method for preparing an anti-reflection film by magnetron sputtering according to claim 6, wherein: During the process of alternately forming the high-refractive-index material layer and the low-refractive-index material layer, the surface of each high-refractive-index material layer is bombarded by an ion source.

8. The method for preparing an anti-reflection film by magnetron sputtering according to claim 7, wherein: The bombardment time of each high refractive index decreases first and then increases in the direction from the substrate to the composite film layer.

9. The method for preparing an anti-reflection film by magnetron sputtering according to claim 5, wherein: During the drying process of the spray-coated AF coating, the temperature is increased using a gradient heating method.

10. An anti-reflection film, characterized in that: The anti-reflection film is prepared by the magnetron sputtering preparation method according to any one of claims 1 to 9, comprising: substrate; A composite film layer is formed on the surface of the substrate, the composite film layer comprising alternately deposited high refractive index material layers and low refractive index material layers, wherein the high refractive index material layer is niobium oxide, tantalum oxide, zirconium oxide, titanium oxide, silicon nitride or aluminum oxide, and the low refractive index material layer is silicon oxynitride, aluminum silicon oxynitride or silicon dioxide.

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