CN105954824B - Reflective obverse mirror of corrosion-resistant height and preparation method thereof - Google Patents

本发明公开了一种耐腐蚀高反光的正面镜，包括玻璃基体与沉积在玻璃基底上的反光涂层，该反光涂层为非晶结构，涂层致密，组成为(Ti_100‑xMe_x)_yB_100‑y，其中，0≤x≤25，50≤y≤80，Me包括Mo或Al；该正面镜具有反光率高、耐腐蚀、耐刮擦的优点。本发明还公开了该正面镜的制备工艺，工艺简单。

The invention discloses a corrosion-resistant and highly reflective front mirror, which comprises a glass substrate and a reflective coating deposited on the glass substrate. The reflective coating has an amorphous structure, and the coating is dense and consists of (Ti _100-x Me _x ) _y B _100‑y , wherein, 0≤x≤25, 50≤y≤80, Me includes Mo or Al; the front mirror has the advantages of high reflectivity, corrosion resistance and scratch resistance. The invention also discloses a preparation process of the front mirror, and the process is simple.

耐腐蚀高反光的正面镜及其制备方法Corrosion-resistant and highly reflective front mirror and preparation method thereof

技术领域technical field

本发明涉及镜子的制备领域，具体涉及耐腐蚀高反光的正面镜及其制备方法。The invention relates to the field of mirror preparation, in particular to a corrosion-resistant and highly reflective front mirror and a preparation method thereof.

背景技术Background technique

镜子是用来反射光线的物品，在很多领域有着重要的应用。如汽车的后视镜、浴室的梳妆镜、科学仪器装备上的反光镜、潜艇的潜望镜等，平板显示器、投影电视、扫描仪、复印机等电子设备中的反光镜等。Mirrors are objects used to reflect light and have important applications in many fields. Such as car rearview mirrors, vanity mirrors in bathrooms, reflectors on scientific instruments and equipment, periscopes on submarines, etc., reflectors in electronic equipment such as flat panel displays, projection TVs, scanners, copiers, etc.

多数镜子的构造都是在玻璃基底上沉积金属如银、铝或铬而形成反射层，之后在反射层上再涂覆聚合物、金属氧化物或氮氧化物等保护层以保护反射层不受机械、化学和其它腐蚀的影响。这种镜子一般都是反射层在镜子的背面上，通常把这种构造的镜子称作—背面镜。Most mirrors are constructed by depositing a metal such as silver, aluminum or chromium on a glass substrate to form a reflective layer, and then coating the reflective layer with a protective layer such as polymer, metal oxide or oxynitride to protect the reflective layer from damage. Effects of mechanical, chemical and other corrosion. This kind of mirror generally has a reflective layer on the back of the mirror, and the mirror of this structure is usually called a back mirror.

这种背面镜在反射光线时，光线要经过玻璃基体两次，一次光线穿过基体玻璃到达反光层，然后经反光层反射的光线再次通过基体玻璃才能入射到人眼。因此存在以下技术不足：一：光线两次穿过玻璃基体削弱了反射能量并且必须使用特别昂贵的玻璃以减少对光线的吸收；二、经玻璃表面和反射层反射的光线会相互干涉，在高清显影上存在不足。When this kind of back mirror reflects light, the light has to pass through the glass substrate twice, once the light passes through the base glass to reach the reflective layer, and then the light reflected by the reflective layer passes through the base glass again to enter the human eye. Therefore, there are the following technical deficiencies: 1. The light passes through the glass substrate twice, which weakens the reflected energy and must use particularly expensive glass to reduce the absorption of light; 2. The light reflected by the glass surface and the reflective layer will interfere with each other. There are deficiencies in the development.

为了克服上述不足，目前的做法是将反光层直接沉积在玻璃表面上形成—正面镜。这种做法的优点是：一、镜子基体可以是任何平整的东西，不在是唯一的玻璃；二、镜子反射率高，高清显影。通常正面镜常用的反光层为Ag层，因为Ag在可见光范围内具有高的反射系数。但Ag反光层本身有许多不足，如Ag比较软，不耐刮擦；Ag易被腐蚀(Ag与空气和水接触时易被氧化；尤其在潮湿的海边，更易与海水中的Cl^-反应而被腐蚀)。In order to overcome the above shortcomings, the current practice is to directly deposit the reflective layer on the glass surface to form a front mirror. The advantages of this method are: 1. The mirror substrate can be any flat thing, not the only glass; 2. The mirror has high reflectivity and high-definition development. Generally, the reflective layer commonly used in the front mirror is an Ag layer, because Ag has a high reflection coefficient in the visible light range. But the Ag reflective layer itself has many deficiencies, such as Ag is relatively soft, not scratch-resistant; Ag is easily corroded (Ag is easily oxidized when it contacts with air and water; especially in humid seaside, it is more likely ^to react with Cl in seawater and corroded).

为了解决Ag反光层的技术缺陷，现有技术中采取了一系列措施，如日本专利JP-A-2003-4919公开了在玻璃上依次序沉积Al₂O₃层/Ag反光层/Al₂O₃层/TiO₂层的叠层结构，利用耐腐蚀性能好的氧化物将Ag反光层隔离保护起来，但是该种方法存在一个困难就是在制备过程中Ag容易被氧化，进而导致Ag的反光性能降低。又如美国专利US5968637、US51525832公开了在玻璃上依次沉积阻挡层/Ag反光层/树脂层或透明聚合物的多层结构，其中阻挡层为氮化物，如TiN、BN、Si₃N₄等，很好的保护了Ag反光层，但该种结构不耐刮擦。为此，专利WO2006041687A1中公开了一种替代反光层Ag的方法，利用CrN_X(X＝0.01～0.5)陶瓷涂层来做反光层，该技术只需一层CrN_x就很好的满足镜子的反光和耐刮擦要求，但该技术也报道了涂层在制备过程中存在着缺陷—涂层表面存在针孔，必须对涂层中的氮含量进行严格控制，所以该技术对制备工艺要求高。另外，当这种Ag反光层的正面镜应用于投影电视、复印机、扫描仪等电子设备时，往往需在反光层(Ag或者Al)上再沉积一层介电层来提高器件的安全性(传统的背面镜不需要，玻璃本身就起到了介电的作用)。但不幸的是该介电层耐刮擦能力弱，很容易产生破损，一旦破损就对反光层的高清显影造成了问题。In order to solve the technical defects of the Ag reflective layer, a series of measures have been taken in the prior art. For example, Japanese patent JP-A-2003-4919 discloses sequentially depositing Al ₂ O ₃ layers/Ag reflective layer/Al ₂ O on glass. The laminated structure of ₃ layers/TiO ₂ layers uses an oxide with good corrosion resistance to isolate and protect the Ag reflective layer, but there is a difficulty in this method that Ag is easily oxidized during the preparation process, which leads to the reflective properties of Ag. reduce. Another example is U.S. Patent No. 5,968,637 and U.S. Patent No. 5,152,5832, which disclose a multilayer structure of sequentially depositing a barrier layer/Ag reflective layer/resin layer or a transparent polymer on glass, wherein the barrier layer is a nitride, such as TiN, BN, Si ₃ N ₄ , etc. The Ag reflective layer is well protected, but this structure is not scratch-resistant. For this reason, the patent WO2006041687A1 discloses a method of replacing Ag in the reflective layer, using CrN _x (X=0.01～0.5) ceramic coating to make the reflective layer, this technology only needs one layer of CrN _x to meet the requirements of the mirror. Reflective and scratch-resistant requirements, but this technology also reports that there are defects in the preparation process of the coating-there are pinholes on the surface of the coating, and the nitrogen content in the coating must be strictly controlled, so this technology has high requirements for the preparation process . In addition, when the front mirror of this Ag reflective layer is applied to electronic devices such as projection TVs, copiers, scanners, it is often necessary to deposit a dielectric layer on the reflective layer (Ag or Al) to improve the safety of the device ( Traditional back mirrors don't need it, the glass itself acts as a dielectric). Unfortunately, the dielectric layer has weak scratch resistance and is prone to damage. Once damaged, it will cause problems for the high-definition development of the reflective layer.

综上所述，正面镜子技术领域，尚缺一种高反光、耐腐蚀、耐刮擦、制备简单的新技术。To sum up, in the technical field of front mirrors, there is still a lack of a new technology that is highly reflective, corrosion-resistant, scratch-resistant, and simple to prepare.

发明内容Contents of the invention

本发明提供了一种具有新型的结构与组成的正面镜，具有反光率高、耐腐蚀、耐刮擦的优点，并通过磁控溅射法制备得到了上述正面镜，制备工艺简单。The invention provides a front mirror with a novel structure and composition, which has the advantages of high reflectivity, corrosion resistance and scratch resistance, and the front mirror is prepared by a magnetron sputtering method, and the preparation process is simple.

本发明公开了一种耐腐蚀高反光的正面镜，包括玻璃基体与沉积在玻璃基底上的反光涂层，所述反光涂层的成分组成为(Ti_100-xMe_x)_yB_100-y，其中，0≤x≤25，50≤y≤80，Me包括Mo或Al；The invention discloses a corrosion-resistant and highly reflective front mirror, which comprises a glass substrate and a reflective coating deposited on the glass substrate, the composition of the reflective coating is (Ti _100-x Me _x ) _y B _100-y , where, 0≤x≤25, 50≤y≤80, Me includes Mo or Al;

所述反光涂层为非晶结构，涂层致密，密度为3.5g/cm³～5.1g/cm³。The reflective coating has an amorphous structure and is dense with a density of 3.5g/cm ³ -5.1g/cm ³ .

作为优选，所述反光涂层的厚度为300～1500nm。Preferably, the reflective coating has a thickness of 300-1500 nm.

作为优选，所述反光涂层的表面为镜面，无针孔或微小颗粒存在，表面粗糙度Ra≤10nm。Preferably, the surface of the reflective coating is a mirror surface without pinholes or tiny particles, and the surface roughness Ra≤10nm.

作为优选，所述反光涂层的电阻率为3×10^-4～5×10^-2Ω.cm。Preferably, the resistivity of the reflective coating is 3×10 ^-4 to 5×10 ^-2 Ω.cm.

作为优选，所述玻璃基体形状为平面板状或曲面状。Preferably, the shape of the glass substrate is a flat plate or a curved surface.

本发明还公开了该耐腐蚀高反光的正面镜的制备方法，采用磁控溅射法沉积反光涂层，具体为：The invention also discloses a method for preparing the corrosion-resistant and highly reflective front mirror, which uses a magnetron sputtering method to deposit a reflective coating, specifically:

(1)玻璃基体清洗；(1) Glass substrate cleaning;

(2)连接电源，将靶材与中频脉冲电源和/或射频电源相连；(2) Connect the power supply, and connect the target with the intermediate frequency pulse power supply and/or radio frequency power supply;

(3)沉积反光涂层，当腔室真空度小于2×10^-5Pa，冲入Ar气并调节溅射气压为0.2～0.7Pa，调整靶材的功率密度8.5W/cm²～20W/cm²，对样品台进行加热和/或施加脉冲负偏压，开启样品挡板，对玻璃基体主表面进行沉积，得到所述的耐腐蚀高反光的正面镜。(3) Deposit reflective coating. When the vacuum degree of the chamber is less than 2×10 ^-5 Pa, pour Ar gas and adjust the sputtering pressure to 0.2-0.7Pa, and adjust the power density of the target to 8.5W/cm ² to 20W/ cm ² , heating the sample stage and/or applying pulsed negative bias, opening the sample baffle, and depositing on the main surface of the glass substrate to obtain the corrosion-resistant and highly reflective front mirror.

作为优选，步骤(1)中，所述的清洗包括化学清洗和等离子辉光刻蚀清洗，将玻璃基体依次放入丙酮、无水乙醇、去离子水中各超声清洗10～20min，然后在温度为80℃～100℃的干燥箱里鼓风干燥1～2h，或采用纯度为99.99％的N₂吹干；将化学清洗后的玻璃基体固定在真空室中可旋转的样品台上，当真空低于1×10^-4Pa后，通入Ar气并维持气压为0.5～2Pa，然后开启电源并同时给基板施加负偏压，利用氩气产生的等离子体对基底刻蚀10～20min，使得基底表面吸附的微小颗粒被刻蚀掉并产生足够多的活性官能团，便于后续反光涂层的沉积附着。As preferably, in step (1), the cleaning includes chemical cleaning and plasma glow etching cleaning, the glass substrate is put into acetone, absolute ethanol, and deionized water successively for ultrasonic cleaning for 10 to 20 minutes, and then the glass substrate is cleaned at a temperature of Blast drying in a drying oven at 80°C to 100°C for 1 to 2 hours, or use _N2 with a purity of 99.99% to blow dry; fix the chemically cleaned glass substrate on a rotatable sample stage in a vacuum chamber, when the vacuum is low After 1×10 ^-4 Pa, introduce Ar gas and maintain the pressure at 0.5-2 Pa, then turn on the power supply and apply a negative bias to the substrate at the same time, use the plasma generated by argon to etch the substrate for 10-20 minutes, so that the substrate The tiny particles adsorbed on the surface are etched away and enough active functional groups are generated to facilitate the deposition and adhesion of subsequent reflective coatings.

作为优选，步骤(2)中，根据反光涂层组成的不同，选用不同的靶材，靶材的组成为(Ti_100-xMe_x)_yB_100-y，其中0≤x≤25，50≤y≤80，Me包括Mo或Al。Preferably, in step (2), different targets are selected according to the composition of the reflective coating, and the composition of the target is (Ti _100-x Me _x ) _y B _100-y , where 0≤x≤25, 50 ≤y≤80, Me includes Mo or Al.

作为优选，步骤(3)中，将样品台加热至30(室温)～300℃。Preferably, in step (3), the sample stage is heated to 30 (room temperature) to 300°C.

作为优选，步骤(3)中，施加-10～-30V的脉冲负偏压。Preferably, in step (3), a pulsed negative bias voltage of -10 to -30V is applied.

传统的银镜存在许多不足，如Ag较软，不耐刮擦，Ag易被腐蚀等。本发明中，以组成为(Ti_100-xMe_x)_yB_100-y的反光涂层替代了传统的Ag层作为镜子涂层，实现了镜子反射性能下降不大的情况下(Ag反光层可见光范围内的反射率为0.95，本发明中反光涂层可见光范围内的反射率为0.65)，克服了传统银镜工艺复杂这一技术不足，并且该正面镜具有较好的耐腐性能和机械性能。经试验，制备得到的正面镜A可以承受300℃的温度，其表面沉积的反光涂层的硬度为15～25GPa，耐刮擦大于300次，对可见光的反光率R为0.5～0.8，折射率n为1.8～2.4。可用于浴室的梳妆镜、潜艇的潜望镜等潮湿环境下需要反光的镜子。Traditional silver mirrors have many disadvantages, such as Ag is soft, not scratch-resistant, and Ag is easily corroded. In the present invention, the reflective coating composed of (Ti _100-x Me _x ) _y B _100-y replaces the traditional Ag layer as the mirror coating, and realizes that the reflective performance of the mirror drops little (Ag reflective layer The reflectivity in the visible light range is 0.95, and the reflective coating in the present invention has a reflectivity in the visible light range of 0.65), which overcomes the technical deficiency of the traditional silver mirror process complexity, and the front mirror has better corrosion resistance and mechanical performance. After testing, the prepared front mirror A can withstand the temperature of 300°C, the hardness of the reflective coating deposited on the surface is 15-25GPa, the scratch resistance is more than 300 times, the reflectance R to visible light is 0.5-0.8, and the refractive index is 0.5-0.8. n is 1.8-2.4. It can be used in bathroom vanity mirrors, submarine periscopes and other mirrors that require reflection in wet environments.

对上述构造的正面镜进行了结构方面的表征和性能方面的测试，表征和测试方法具体说明如下：Structural characterization and performance testing have been carried out on the front mirror with the above structure. The characterization and testing methods are specifically described as follows:

镜子涂层成分测定：利用FEI QuantaTM 250FEG的EDS功能测量涂层的成分组成，其配置EDAX Si(Li)探头，通过ZAF校准，每个样品选定一个面积不小于40mm²区域，测量其成分的平均值。Determination of mirror coating composition: Use the EDS function of FEI QuantaTM 250FEG to measure the composition of the coating. It is equipped with an EDAX Si(Li) probe and calibrated by ZAF. For each sample, select an area with an area not less than 40mm ² to measure its composition. average value.

镜子涂层密度测定：采用在规则的基体上沉积3～5μm厚的涂层，通过计算涂层的体积和称量涂层的质量，根据密度计算公式质量除以体积计算而得到。Determination of mirror coating density: by depositing a 3-5 μm thick coating on a regular substrate, by calculating the volume of the coating and weighing the quality of the coating, it is obtained by dividing the mass by the volume according to the density calculation formula.

镜子涂层晶体结构表征：采用德国Bruker D8Advance X射线衍射仪(XRD)，利用CuKα射线入射，θ/θ模式，X射线管控制在40kV和40mA，测量各涂层的晶体结构。Crystal structure characterization of the mirror coating: German Bruker D8Advance X-ray diffractometer (XRD) was used to measure the crystal structure of each coating using CuKα ray incidence, θ/θ mode, and X-ray tube controlled at 40kV and 40mA.

镜子涂层光学特性表征：采用Perkin Elmer Lambda 950型号的紫外-可见分光光度计测量其反射率和光学常数，选用白板作为反射的标准。Characterization of the optical properties of the mirror coating: the reflectance and optical constants were measured with a Perkin Elmer Lambda 950 UV-Vis spectrophotometer, and a white board was selected as the reflection standard.

镜子涂层的耐腐测试：采用美国翁开尔公司Q-FOG CCT1100设备对该涂层的耐盐雾能力进行测试，其中盐雾浓度为5wt％，温度为35℃，湿度为60％。Corrosion resistance test of the mirror coating: The salt spray resistance of the coating was tested using the Q-FOG CCT1100 equipment of the American Onkel Company, in which the salt spray concentration was 5wt%, the temperature was 35°C, and the humidity was 60%.

镜子涂层的硬度测量：在MTS NANO G200纳米压痕仪上进行。其中硬度测试采用Berkovich金刚石压头，为了消除基片效应和表面粗糙度的影响，最大压入深度约为膜厚的1/10，载荷随压入深度而改变，每个样品测量10个矩阵点后取平均值。Hardness measurement of mirror coating: carried out on MTS NANO G200 nanoindenter. Among them, Berkovich diamond indenter is used for hardness test. In order to eliminate the influence of substrate effect and surface roughness, the maximum indentation depth is about 1/10 of the film thickness, and the load changes with the indentation depth. Each sample measures 10 matrix points Then take the average value.

镜面粗糙度测量：表面粗糙度借助于AFM(原子力显微镜)来测量，选用ASTME-42.14STM/AFM标准。Mirror surface roughness measurement: The surface roughness is measured by means of AFM (atomic force microscope), using the ASTME-42.14STM/AFM standard.

镜面耐刮擦测量：为了测量耐刮擦性，将尖端半径50μm的金刚石针在镜面上以50g承重和1.5cm/s的速度往复移动，当涂层出现剥落时往复移动的次数作为镜面耐刮擦能力衡量的标准。Mirror surface scratch resistance measurement: In order to measure the scratch resistance, a diamond needle with a tip radius of 50 μm reciprocates on the mirror surface with a load of 50g and a speed of 1.5cm/s. When the coating peels off, the number of reciprocating movements is used as the mirror surface scratch resistance A measure of rubbing ability.

与现有技术相比，本发明具有如下优点：Compared with prior art, the present invention has following advantage:

本发明公开的正面镜，用硼化物陶瓷涂层直接替代Ag层作为镜子的反光层，克服了传统Ag镜不耐腐或制备工艺复杂技术不足。该硼化物陶瓷涂层作为镜子反光层，高清显影，反射率为0.65，耐刮擦大于200次、耐盐雾1000h腐蚀、硬度为28GPa，适合腐蚀环境下需要防腐的镜子领域。In the front mirror disclosed by the invention, the boride ceramic coating is used to directly replace the Ag layer as the reflective layer of the mirror, which overcomes the shortcomings of traditional Ag mirrors which are not resistant to corrosion or have complicated preparation techniques. The boride ceramic coating is used as the reflective layer of the mirror, with high-definition development, a reflectivity of 0.65, a scratch resistance of more than 200 times, a corrosion resistance of salt spray for 1000 hours, and a hardness of 28GPa. It is suitable for the field of mirrors that require anti-corrosion in corrosive environments.

附图说明Description of drawings

图1为本发明的正面镜的截面结构示意图，图中，1-玻璃基体，2-反光涂层；Fig. 1 is the cross-sectional structure schematic diagram of front mirror of the present invention, among the figure, 1-glass matrix, 2-reflective coating;

图2为实施例1制备的正面镜表面沉积的反光涂层的表面SEM形貌图。Fig. 2 is the SEM topography of the surface of the reflective coating deposited on the surface of the front mirror prepared in Example 1.

具体实施方式detailed description

下面通过具体实施例，并结合附图，对本发明的技术方案作进一步的具体说明。The technical solutions of the present invention will be further specifically described below through specific embodiments and in conjunction with the accompanying drawings.

实施例1Example 1

本发明的正面镜采用物理气相磁控溅射法沉积，如图1所示，首先将平面板状玻璃基体1依次放入丙酮、无水乙醇、去离子水中各超声清洗15min，接着在温度为100℃的干燥箱里鼓风2h；然后将其固定在真空室中可旋转的样品台上，利用氩气产生的等离子体对其刻蚀10min。当腔室真空度小于2×10^-5Pa，冲入Ar气并调节溅射气压为0.5Pa，选用组成为(Ti₇₅Al₂₅)₅₀B₅₀的靶材并与脉冲电源相连，调整靶材的功率密度为8.5W/cm²，并对基体进行了接地和加热100℃处理，之后开启挡板，对玻璃基体1表面进行沉积，得到组成为(Ti₇₅Al₂₅)₅₀B₅₀反光涂层2。The front mirror of the present invention is deposited by physical vapor phase magnetron sputtering, as shown in Figure 1, at first the flat plate glass substrate 1 is put into successively ultrasonic cleaning of acetone, dehydrated alcohol, and deionized water for 15min, and then heated at a temperature of Blow air in a drying oven at 100°C for 2 hours; then fix it on a rotatable sample stage in a vacuum chamber, and etch it for 10 minutes with plasma generated by argon. When the vacuum degree of the chamber is less than 2×10 ^-5 Pa, pour Ar gas and adjust the sputtering pressure to 0.5Pa, select a target with a composition of (Ti ₇₅ Al ₂₅ ) ₅₀ B ₅₀ and connect it to a pulse power supply, adjust the target The power density is 8.5W/cm ² , and the substrate is grounded and heated at 100°C, then the baffle is opened, and the surface of the glass substrate 1 is deposited to obtain a reflective coating with a composition of (Ti ₇₅ Al ₂₅ ) ₅₀ B ₅₀ 2.

经X射线衍射仪(XRD)检测该反光涂层为非晶结构。涂层致密，密度4.5g/cm³。涂层的电阻率为3×10^-4Ω.cm，表面粗糙度Ra≦10nm。利用SEM电镜对涂层2的表面进行观察，如附图2所示，涂层表面不存在针孔或微小颗粒。测试涂层的硬度为15GPa，涂层的反光率为0.7。当涂层厚度为300nm时，涂层耐刮擦测试值为50次，厚度为800nm时耐刮擦测试值为130次；盐雾测试表明，800nm厚的涂层耐1000h盐雾后表面仍然光亮，未出现明显的腐蚀坑道。The reflective coating has an amorphous structure as detected by an X-ray diffractometer (XRD). The coating is dense with a density of 4.5g/cm ³ . The resistivity of the coating is 3×10 ^-4 Ω.cm, and the surface roughness Ra≦10nm. The surface of the coating 2 was observed with a SEM electron microscope. As shown in FIG. 2 , there were no pinholes or tiny particles on the coating surface. The hardness of the test coating is 15GPa, and the reflectance of the coating is 0.7. When the coating thickness is 300nm, the scratch resistance test value of the coating is 50 times, and the scratch resistance test value is 130 times when the thickness is 800nm; the salt spray test shows that the surface of the 800nm thick coating is still bright after 1000h salt spray resistance , no obvious corrosion pits appeared.

实施例2Example 2

本发明的正面镜采用物理气相磁控溅射法沉积，如图1所示，首先将平面板状玻璃基体1依次放入丙酮、无水乙醇、去离子水中各超声清洗20min，接着在温度为80℃的干燥箱里鼓风2h；然后将其固定在真空室中可旋转的样品台上，利用氩气产生的等离子体对其刻蚀20min。当腔室真空度小于1×10^-5Pa，冲入Ar气并调节溅射气压为0.7Pa，选用组成为(Ti₉₂Mo₈)₇₀B₃₀的靶材并与脉冲电源相连，调整靶材的功率密度为20W/cm²，并对基体进行了-20V直流偏压和加热300℃处理，之后开启挡板，对玻璃基体1表面进行沉积，得到组成为(Ti₉₂Mo₈)₇₀B₃₀反光涂层2。The front mirror of the present invention is deposited by physical vapor-phase magnetron sputtering, as shown in Figure 1, at first the planar glass substrate 1 is put into acetone, dehydrated alcohol and deionized water successively for ultrasonic cleaning for 20min, then at a temperature of Blow air in a drying oven at 80°C for 2 hours; then fix it on a rotatable sample stage in a vacuum chamber, and etch it for 20 minutes with plasma generated by argon. When the vacuum degree of the chamber is less than 1×10 ^-5 Pa, pour Ar gas and adjust the sputtering pressure to 0.7Pa, select a target with a composition of (Ti ₉₂ Mo ₈ ) ₇₀ B ₃₀ and connect it to a pulse power supply, adjust the target The power density is 20W/cm ² , and the substrate is subjected to -20V DC bias and heated at 300°C, then the baffle is opened, and the surface of the glass substrate 1 is deposited to obtain a composition of (Ti ₉₂ Mo ₈ ) ₇₀ B ₃₀ Reflective coating2.

经X射线衍射仪(XRD)检测，反光涂层为非晶结构。涂层非常致密，密度为5.1g/cm³。涂层的电阻率为7.3×10^-3Ω.cm；表面粗糙度为Ra≦20nm。利用SEM电镜对反光涂层的表面进行观察，涂层表面不存在针孔或微小颗粒。测试涂层的硬度为20GPa，涂层的反光率为0.75；涂层2厚度为1000nm时耐刮擦测试值为208次；盐雾测试表明，耐1000h盐雾涂层表面仍然光亮，1200h涂层局部出现了腐蚀坑道。Detected by X-ray diffractometer (XRD), the reflective coating has an amorphous structure. The coating is very dense with a density of 5.1 g/cm ³ . The resistivity of the coating is 7.3×10 ^-3 Ω.cm; the surface roughness is Ra≦20nm. The surface of the reflective coating is observed with a SEM electron microscope, and there are no pinholes or tiny particles on the surface of the coating. The hardness of the test coating is 20GPa, and the reflectance of the coating is 0.75; when the thickness of the coating 2 is 1000nm, the scratch resistance test value is 208 times; the salt spray test shows that the surface of the 1000h salt spray resistant coating is still bright, and the 1200h coating Corrosion pits appeared locally.

实施例3Example 3

本发明的正面镜采用物理气相磁控溅射法沉积，如图1所示，首先将平面板状玻璃基体1依次放入丙酮、无水乙醇、去离子水中各超声清洗10min，然后采用纯度为99.99％的高纯N₂吹干；然后将其固定在真空室中可旋转的样品台上，利用氩气产生的等离子体对其刻蚀15min。当腔室真空度小于3.6×10^-5Pa，冲入Ar气并调节溅射气压为0.5Pa，选用组成为Ti₅₀B₅₀的靶材并与脉冲电源相连，调整靶材的功率密度为13W/cm²，并对基体进行了-30V的脉冲负偏压和加热200℃处理，之后开启挡板，对玻璃基体1表面进行沉积，得到组成为Ti₅₀B₅₀的反光涂层2。The front mirror of the present invention is deposited by physical vapor phase magnetron sputtering, as shown in Figure 1, at first the planar plate glass substrate 1 is put into acetone, absolute ethanol, and each ultrasonic cleaning in deionized water successively for 10min, and then adopts a method with a purity of 99.99% high-purity N ₂ was blown dry; then it was fixed on a rotatable sample stage in a vacuum chamber, and it was etched for 15 minutes by plasma generated by argon gas. When the vacuum degree of the chamber is less than 3.6×10 ^-5 Pa, pour Ar gas and adjust the sputtering pressure to 0.5Pa, select a target composed of Ti ₅₀ B ₅₀ and connect it to a pulse power supply, and adjust the power density of the target to 13W /cm ² , and the substrate was treated with pulse negative bias of -30V and heated at 200°C, and then the baffle was opened to deposit on the surface of the glass substrate 1 to obtain a reflective coating 2 with a composition of Ti ₅₀ B ₅₀ .

经X射线衍射仪(XRD)检测，涂层为非晶结构，涂层致密，密度为4.6g/cm³。涂层的电阻率为7.3×10^-4Ω.cm；表面粗糙度为Ra≦15nm。利用SEM电镜对涂层2的表面进行观察，涂层表面不存在针孔或微小颗粒。测试涂层的硬度为25GPa，涂层的反光率为0.53；涂层厚度为1500nm时，耐刮擦测试值为250次；盐雾测试表明，耐1200h盐雾涂层表面仍然光亮，未出现明显的腐蚀坑道。As detected by X-ray diffractometer (XRD), the coating has an amorphous structure and is dense with a density of 4.6 g/cm ³ . The resistivity of the coating is 7.3×10 ^-4 Ω.cm; the surface roughness is Ra≦15nm. The surface of the coating 2 was observed with a SEM electron microscope, and there were no pinholes or tiny particles on the coating surface. The hardness of the test coating is 25GPa, and the reflectance of the coating is 0.53; when the thickness of the coating is 1500nm, the scratch resistance test value is 250 times; the salt spray test shows that the surface of the 1200h salt spray resistant coating is still bright without obvious corrosion pits.

实施例4Example 4

本发明的正面镜采用物理气相磁控溅射法沉积，如图1所示，将平面板状玻璃基体1依次放入丙酮、无水乙醇、去离子水中各超声清洗15min，然后在温度为80℃的干燥箱里鼓风2h；然后将其固定在真空室中可旋转的样品台上，利用氩气产生的等离子体对其刻蚀20min。当腔室真空度小于1×10^-5Pa，冲入Ar气并调节溅射气压为0.5Pa，选用组成为Ti₆₀B₄₀的靶材并与脉冲电源相连，调整靶材的功率密度为8.5W/cm²，并对基体进行了-30V的脉冲负偏压和加热200℃处理，之后开启挡板，对玻璃基体1表面进行沉积，得到组成为Ti₆₀B₄₀的反光涂层2。The front mirror of the present invention is deposited by physical vapor-phase magnetron sputtering. As shown in Figure 1, the flat plate glass substrate 1 is put into acetone, dehydrated alcohol and deionized water successively for ultrasonic cleaning for 15min, and then heated at a temperature of 80 ℃ in a drying oven for 2 hours; then it was fixed on a rotatable sample stage in a vacuum chamber, and it was etched for 20 minutes by plasma generated by argon gas. When the vacuum degree of the chamber is less than 1×10 ^-5 Pa, pour Ar gas and adjust the sputtering pressure to 0.5 Pa, select a target composed of Ti ₆₀ B ₄₀ and connect it to a pulse power supply, and adjust the power density of the target to 8.5 W/cm ² , and the substrate was subjected to -30V pulse negative bias and heated at 200°C, and then the baffle was opened to deposit on the surface of the glass substrate 1 to obtain a reflective coating 2 composed of Ti ₆₀ B ₄₀ .

经X射线衍射仪(XRD)检测，涂层为非晶结构，涂层非常致密，密度为4.8g/cm³。涂层的电阻率为5.3×10^-4Ω.cm；表面粗糙度为Ra≦10nm。利用SEM电镜对涂层2的表面进行观察，涂层表面不存在针孔或微小颗粒。测试涂层的硬度为25GPa，涂层的反光率为0.6；涂层1500nm厚时，耐刮擦测试值为200次；盐雾测试表明，耐900h盐雾涂层表面仍然光亮，1000h出现局部的腐蚀坑道。As detected by X-ray diffractometer (XRD), the coating has an amorphous structure and is very dense with a density of 4.8 g/cm ³ . The resistivity of the coating is 5.3×10 ^-4 Ω.cm; the surface roughness is Ra≦10nm. The surface of the coating 2 was observed with a SEM electron microscope, and there were no pinholes or tiny particles on the coating surface. The hardness of the test coating is 25GPa, and the reflectance of the coating is 0.6; when the coating is 1500nm thick, the scratch resistance test value is 200 times; the salt spray test shows that the surface of the 900h salt spray resistant coating is still bright, and local scratches appear after 1000h Corrosion pits.

实施例5Example 5

本发明的正面镜采用物理气相磁控溅射法沉积，如图1所示将平面板状玻璃基体1依次放入丙酮、无水乙醇、去离子水中各超声清洗20min，然后在温度为80℃的干燥箱里鼓风2h；然后将其固定在真空室中可旋转的样品台上，利用氩气产生的等离子体对其刻蚀20min。当腔室真空度小于1×10^-5Pa，冲入Ar气并调节溅射气压为0.2Pa，选用组成为(Ti₉₀Al₁₀)₈₀B₂₀的靶材并与脉冲电源相连，调整靶材的功率密度为16W/cm²，并对基体进行了-30V的负偏压和加热200℃处理，之后开启挡板，对玻璃基体1表面进行得到组成为(Ti₉₀Al₁₀)₈₀B₂₀的反光涂层2。The front mirror of the present invention is deposited by physical vapor-phase magnetron sputtering. As shown in Figure 1, the flat plate glass substrate 1 is successively put into acetone, absolute ethanol, and deionized water for ultrasonic cleaning for 20 minutes, and then at a temperature of 80 ° C. Blow air in a dry oven for 2 hours; then fix it on a rotatable sample stage in a vacuum chamber, and etch it for 20 minutes with plasma generated by argon gas. When the chamber vacuum is less than 1×10 ^-5 Pa, pour in Ar gas and adjust the sputtering pressure to 0.2Pa, select a target with a composition of (Ti ₉₀ Al ₁₀ ) ₈₀ B ₂₀ and connect it to a pulse power supply, adjust the target The power density is 16W/cm ² , and the substrate is subjected to a negative bias voltage of -30V and heated at 200°C. After that, the baffle is opened, and the surface of the glass substrate 1 is treated to obtain a composition of (Ti ₉₀ Al ₁₀ ) ₈₀ B ₂₀ Reflective coating2.

经X射线衍射仪(XRD)检测，涂层为非晶结构，涂层非常致密，密度为5.0g/cm³。涂层的电阻率为3.3×10^-3Ω.cm；表面粗糙度为Ra≦10nm。利用SEM电镜对涂层2的表面进行观察，涂层表面不存在针孔或微小颗粒。测试涂层的硬度为17GPa，涂层的反光率为0.75，1500nm厚耐刮擦测试值为150次；盐雾测试表明，涂层耐500h盐雾表面仍然光亮，未出现明显的腐蚀坑道，但700h涂层局部发生腐蚀脱落。As detected by X-ray diffractometer (XRD), the coating has an amorphous structure and is very dense with a density of 5.0 g/cm ³ . The resistivity of the coating is 3.3×10 ^-3 Ω.cm; the surface roughness is Ra≦10nm. The surface of the coating 2 was observed with a SEM electron microscope, and there were no pinholes or tiny particles on the coating surface. The hardness of the test coating is 17GPa, the reflectance of the coating is 0.75, and the scratch resistance test value of 1500nm thick is 150 times; the salt spray test shows that the surface of the coating is still bright after 500h of salt spray resistance, and no obvious corrosion pits appear, but After 700h, the coating partially corroded and peeled off.

此外应理解，在阅读了本发明说明书的上述内容之后，本领域技术人员可以对本发明作各种改动或修改，这些等同的技术方案同样落于本申请所附权利要求书所限定的范围。In addition, it should be understood that those skilled in the art may make various changes or modifications to the present invention after reading the above contents of the present specification, and these equivalent technical solutions also fall within the scope defined by the appended claims of the present application.