WO2021047643A1 - Reinforced nanofilm for outer cover of electronic equipment and preparation method therefor and use thereof - Google Patents

Abstract

Disclosed are a reinforced nanofilm for an outer cover of an electronic equipment and a preparation method therefor and the use thereof, wherein the reinforced nanofilm comprises C, H and at least one doping element, and is formed by depositing on the surface of a substrate by means of PECVD technology with a hydrocarbon gas CxHy and at least one doping gas as reaction gas raw materials, wherein the doping gas provides the doping element, and the reinforced nanofilm is suitable for use in electronic equipment to enhance the rigidity of the surface of the electronic equipment.

Description

电子设备外盖增强纳米膜及其制备方法和应用Electronic equipment outer cover reinforced nano-membrane and preparation method and application thereof 技术领域Technical field

本发明涉及表面改性领域，更进一步，涉及一电子设备外盖增强纳米膜及其制备方法和应用。The invention relates to the field of surface modification, and further relates to an electronic device outer cover reinforced nano-membrane, and a preparation method and application thereof.

背景技术Background technique

5G网络作为第五代移动通信网络，目前正迅速走向商业化，一些大的运营商试用测试已经进入最后阶段。虽然5G频率还未统一，但其采用电磁波频段全部在3GHz以上，比如中国工信部为3 000～3 600MHz与4 800～5 000MHz；欧盟爱立信则用3.5GHz频段的100MHz带宽；美国苹果公司5G手机将支持高频段从几百兆赫(MHz)到几十吉赫(GHz)的毫米波。相应地，随之而来的是对更高性能、高传输速率的的5G手机巨大市场需求，给电子产品行业带来了巨大的机遇和挑战。比如5G手机的后盖不能再采用质感好、轻薄的金属材料，因为金属材料对5G高频天线信号有明显的吸收，此外，5G手机天线结构与安装比4G要复杂，如采用金属后盖，则电磁波的接收与发射在金属中衰减损失很大，开发新的手机后盖材料以满足5G需求成为手机配件供应商争相研发的热点。消费电子行业的特性决定了手机厂商及其相关供应商必须不断跟进最新技术的发展和市场需求，手机后盖材料的选择也是如此。后盖材料经历了塑料材质，全金属时代，已经开始进入玻璃、复合材料、陶瓷等新兴材料时代。As the fifth-generation mobile communication network, 5G network is currently rapidly moving towards commercialization, and some large operators have entered the final stage of trial testing. Although 5G frequencies have not yet been unified, the electromagnetic wave frequency bands used are all above 3 GHz. For example, the Ministry of Industry and Information Technology of China is 3 000-3 600 MHz and 4 800-5 000 MHz; the European Union Ericsson uses the 100 MHz bandwidth of the 3.5 GHz band; the US Apple 5G mobile phone will It supports millimeter waves in high frequency bands from hundreds of megahertz (MHz) to tens of gigahertz (GHz). Correspondingly, there is a huge market demand for 5G mobile phones with higher performance and high transmission rate, which brings huge opportunities and challenges to the electronic product industry. For example, the back cover of 5G mobile phone can no longer use good-quality, light and thin metal materials, because metal materials have obvious absorption of 5G high-frequency antenna signals. In addition, the structure and installation of 5G mobile phone antennas are more complicated than 4G. If a metal back cover is used, Therefore, the reception and transmission of electromagnetic waves have a large attenuation loss in metal, and the development of new mobile phone back cover materials to meet the needs of 5G has become a hot spot for mobile phone accessory suppliers to compete for research and development. The characteristics of the consumer electronics industry determine that mobile phone manufacturers and their related suppliers must constantly follow the development of the latest technology and market demand, as is the choice of mobile phone back cover materials. The back cover material has experienced plastic materials, and the era of all metals has begun to enter the era of emerging materials such as glass, composite materials, and ceramics.

此外，无线充电技术同样要求手机后盖对电磁屏蔽要弱，由于金属对电磁波的屏蔽特性，电磁波无法很好通过金属机壳，能量损耗大，所以金属机壳不适宜无线充电技术。手机后盖“去金属化”已经成为不可逆转的行业趋势。陶瓷手机后盖采用纳米级四方氧化锆多晶体陶瓷(TZP)为原材料，由于具有美观精致、耐磨耐腐蚀、高抗冲击强度、低电磁信号屏蔽性等优良特性而深受广大消费者青睐，但陶瓷手机后盖在成型烧结、精密加工过程中的低良品率问题严重限制了陶瓷手机后盖的推广发展，其成本相比于玻璃至少要高出2倍；3D曲面复合材料手机后盖它是由原材料复合板如PC+PMMA采用多道工序高压空气热弯成型，但 其硬度偏低、手感不如玻璃。总的来说，陶瓷、玻璃材质将成为手机后盖的最佳备选材料之一。但这两种材料都存在不耐摔的特点，为了避免手机后盖被摔伤、摔裂，人们常常给手机套上一层塑料材质的保护壳，但这种办法是以损失用户体验、降低手机设计美感为代价，且成本也不低。In addition, the wireless charging technology also requires that the back cover of the mobile phone has weak electromagnetic shielding. Due to the shielding characteristics of metal to electromagnetic waves, electromagnetic waves cannot pass through the metal case well, and the energy loss is large, so the metal case is not suitable for wireless charging technology. "Demetalization" of the back cover of mobile phones has become an irreversible industry trend. The back cover of ceramic mobile phone uses nano-grade tetragonal zirconia polycrystalline ceramics (TZP) as raw materials. It is favored by consumers because of its beautiful and exquisite characteristics, wear-resistant and corrosion-resistant, high impact strength, and low electromagnetic signal shielding. However, the low-yield rate of the ceramic mobile phone back cover in the molding, sintering and precision machining process has severely restricted the promotion and development of the ceramic mobile phone back cover, and its cost is at least 2 times higher than that of glass; it is a 3D curved composite mobile phone back cover. It is made of raw material composite boards such as PC+PMMA by multi-process high-pressure air bending forming, but its hardness is low and the hand feel is not as good as glass. In general, ceramic and glass materials will become one of the best alternative materials for the back cover of mobile phones. However, both of these two materials are not resistant to falling. In order to prevent the back cover of the mobile phone from being broken or cracked, people often put a layer of plastic protective shell on the mobile phone, but this method is to lose the user experience and reduce Mobile phone design is at the expense of aesthetics, and the cost is not low.

另一方面，电子设备后盖，通常带有弧形的边，而这些边缘也是保护较少的区域，在跌落后者撞击时，边缘位置总是最先受损。根据Griffith微裂纹理论，实际材料中总存在许多细小的裂纹或缺陷，在外力作用下，这些裂纹和缺陷附近就会产生应力集中现象，当应力达到一定程度时，裂纹就开始扩展而导致断裂，因此电子设备的后盖的边缘区域也是最先出现问题的地方，而对于现有的外盖制造技术，并没有很好的方式来预防或者改善这样的问题。On the other hand, the back cover of electronic equipment usually has curved edges, and these edges are also areas with less protection. When a person is hit by a fall, the edge position is always the first to be damaged. According to Griffith micro-crack theory, there are always many small cracks or defects in actual materials. Under the action of external force, stress concentration will occur near these cracks and defects. When the stress reaches a certain level, the cracks will start to expand and cause fractures. Therefore, the edge area of the back cover of the electronic device is also the first place where the problem occurs, and for the existing outer cover manufacturing technology, there is no good way to prevent or improve such a problem.

发明内容Summary of the invention

本发明的一个优势在于提供一电子设备外盖增强纳米膜及其制备方法和应用，其利用等离子体增强化学气相沉积(PECVD)方法在一电子设备外盖表面形成一类金刚石薄膜(Diamond Like Carbon，DLC)，以改善所述电子设备外盖的表面性能。An advantage of the present invention is to provide an electronic device outer cover reinforced nano film and its preparation method and application, which use plasma enhanced chemical vapor deposition (PECVD) method to form a diamond-like carbon film (Diamond Like Carbon) on the surface of an electronic device outer cover. , DLC) to improve the surface performance of the outer cover of the electronic device.

本发明的一个优势在于提供一电子设备外盖增强纳米膜及其制备方法和应用，其中所述电子设备外盖增强纳米膜能够改善所述电子设备外盖的耐磨性能，提高耐摔次数，减少残余应力。An advantage of the present invention is to provide an electronic device outer cover reinforced nano-membrane, and a preparation method and application thereof, wherein the electronic device outer cover-reinforced nano film can improve the wear resistance of the electronic device outer cover and increase the number of times of falling resistance. Reduce residual stress.

本发明的一个优势在于提供一电子设备外盖增强纳米膜及其制备方法和应用，其中所述增强纳米膜沉积于所述电子设备外盖的表面，相互结合度高，连接稳定。An advantage of the present invention is to provide an electronic device outer cover reinforced nano film and its preparation method and application, wherein the enhanced nano film is deposited on the surface of the electronic device outer cover, with high mutual bonding and stable connection.

本发明的一个优势在于提供一电子设备外盖增强纳米膜及其制备方法和应用，其中所述增强纳米膜能够沉积于外盖的边缘区域，减少外盖边缘区域产生Griffith裂纹，也就是说，所述增强纳米膜可以全面地覆盖所述外盖的表面。An advantage of the present invention is to provide an electronic device outer cover reinforced nano film and its preparation method and application, wherein the reinforced nano film can be deposited on the edge area of the outer cover to reduce Griffith cracks in the edge area of the outer cover, that is, The reinforced nano film can completely cover the surface of the outer cover.

本发明的一个优势在于提供一电子设备外盖增强纳米膜及其制备方法和应用，其中PECVD沉积过程温度较低，不影响电子设备的性能，也就是说，所述外盖增强能够直接在所述外盖的表面沉积形成，也可以在所述外盖安装于所述电子设备，在所述电子设备的外表面沉积形成，制造工艺灵活，适用范围广泛。One advantage of the present invention is to provide an electronic device outer cover reinforced nano film and its preparation method and application, wherein the PECVD deposition process temperature is relatively low and does not affect the performance of the electronic device, that is, the outer cover enhancement can be directly in the place. The surface of the outer cover is deposited and formed, and it can also be installed on the electronic device on the outer cover, and deposited on the outer surface of the electronic device. The manufacturing process is flexible and the application range is wide.

本发明的一个优势在于提供一电子设备外盖增强纳米膜及其制备方法和应 用，其中PECVD沉积过程反应过程沉积效率高，成膜时间较短。An advantage of the present invention is to provide an electronic device outer cover reinforced nano film and its preparation method and application, wherein the PECVD deposition process has high reaction process deposition efficiency and short film formation time.

本发明的一个优势在于提供一电子设备外盖增强纳米膜及其制备方法和应用，其采用碳原子数为1-6的烷烃、烯烃、炔烃作为反应气体原料来形成DLC膜。One advantage of the present invention is to provide an electronic device outer cover reinforced nano-membrane and its preparation method and application, which use alkanes, alkenes, and alkynes with carbon atoms of 1 to 6 as raw materials for reaction gas to form DLC membranes.

本发明的一个优势在于提供一电子设备外盖增强纳米膜及其制备方法和应用，其加入掺杂气体原料与反应气体原料共同进行PECVD沉积反应，以在DLC膜中掺入C、H之外的其它元素，来改变所述DLC膜的性能。One advantage of the present invention is to provide an electronic device outer cover reinforced nano film and its preparation method and application, which add dopant gas raw materials and reactive gas raw materials to perform PECVD deposition reaction together, so as to dope C and H in the DLC film. Other elements to change the performance of the DLC film.

本发明的一个优势在于提供一电子设备外盖增强纳米膜及其制备方法和应用，其中在一些实施例中，所述掺杂元素选自Si、N、F、B中的一种或多种。An advantage of the present invention is to provide an electronic device outer cover reinforced nano film and its preparation method and application. In some embodiments, the doping element is selected from one or more of Si, N, F, and B .

本发明的一个优势在于提供一电子设备外盖增强纳米膜及其制备方法和应用，其中在一些实施例中，掺杂Si元素的所述掺杂气体原料可以是含硅有机化合物，包括有机直链硅氧烷、环硅氧烷、烷氧基硅烷、含不饱和碳碳双键硅氧烷。An advantage of the present invention is to provide an electronic device outer cover reinforced nano film and its preparation method and application. In some embodiments, the doping gas raw material doped with Si element may be a silicon-containing organic compound, including organic direct Chain siloxanes, cyclosiloxanes, alkoxysilanes, siloxanes containing unsaturated carbon-carbon double bonds.

本发明的一个优势在于提供一电子设备外盖增强纳米膜及其制备方法和应用，其中在一些实施例中，掺杂N元素的所述掺杂气体原料是N ₂、NO ₂、含氮碳氢化合物。 An advantage of the present invention is to provide an electronic device outer cover reinforced nano film and its preparation method and application. In some embodiments, the dopant gas raw material doped with N element is N ₂ , NO ₂ , nitrogen-containing carbon Hydrogen compounds.

本发明的一个优势在于提供一电子设备外盖增强纳米膜及其制备方法和应用，其中在一些实施例中，掺杂F元素的所述掺杂气体原料是氟碳气体，进一步地，选自四氟化碳、八氟丙烯、八氟环丁烷。An advantage of the present invention is to provide an electronic device outer cover reinforced nano-membrane and its preparation method and application. In some embodiments, the doping gas raw material doped with the F element is a fluorocarbon gas, and is further selected from Carbon tetrafluoride, octafluoropropene, octafluorocyclobutane.

本发明的一个优势在于提供一电子设备外盖增强纳米膜及其制备方法和应用，其中在一些实施例中，掺杂B元素的所述掺杂气体原料是常压下沸点低于300℃的硼烷，进一步地，选自戊硼烷、己硼烷。An advantage of the present invention is to provide an electronic device outer cover reinforced nano-membrane and its preparation method and application. In some embodiments, the dopant gas raw material doped with element B has a boiling point lower than 300°C under normal pressure. Borane is further selected from pentaborane and hexaborane.

本发明的一个优势在于提供一电子设备外盖增强纳米膜及其制备方法和应用，其利用射频和高压脉冲共同作用来完成PECVD沉积过程。One advantage of the present invention is to provide an electronic device outer cover reinforced nano film and its preparation method and application, which utilize the combined action of radio frequency and high voltage pulse to complete the PECVD deposition process.

本发明的一个优势在于提供一电子设备外盖增强纳米膜及其制备方法和应用，其中射频和高压脉冲的共同作用增强沉积效率，使得在电子设备外盖表面能够有效沉积形成保护膜。An advantage of the present invention is to provide an electronic device outer cover reinforced nano film and its preparation method and application, wherein the combined action of radio frequency and high voltage pulse enhances the deposition efficiency, so that a protective film can be effectively deposited on the surface of the electronic device outer cover.

本发明的一个优势在于提供一电子设备外盖增强纳米膜及其制备方法和应用，其利用低功率射频放电维持等离子体环境，抑制高压放电过程的弧光放电，由此提高化学沉积效率。An advantage of the present invention is to provide an electronic device outer cover reinforced nano-film and its preparation method and application, which use low-power radio frequency discharge to maintain a plasma environment and suppress arc discharge in the high-voltage discharge process, thereby improving the efficiency of chemical deposition.

本发明的一个优势在于提供一电子设备外盖增强纳米膜及其制备方法和应 用，其在电子设备外盖表面直接沉积形成膜层，不需要进行漫长的离子交换过程，也不需要进行离子浴，制备过程简单、反应时间短、成本较低。One advantage of the present invention is to provide an electronic device outer cover reinforced nano-membrane and its preparation method and application, which are directly deposited on the surface of the electronic device outer cover to form a film layer without the need for a long ion exchange process or an ion bath. , The preparation process is simple, the reaction time is short, and the cost is low.

本发明的一个优势在于提供一电子设备外盖增强纳米膜及其制备方法和应用，其能够通过控制射频和高压脉冲的放电特性、反应气体的流量以及镀膜时间等工艺参数，来获得目标钢化外盖增强纳米膜。An advantage of the present invention is to provide an electronic device outer cover reinforced nano film and its preparation method and application, which can obtain the target tempered outer film by controlling the process parameters such as the discharge characteristics of radio frequency and high voltage pulses, the flow rate of the reactive gas, and the coating time. Cover reinforced nano-membrane.

本发明的一个优势在于提供一电子设备外盖增强纳米膜及其制备方法和应用，其中在一些实施例中，所述电子设备外盖是玻璃或者陶瓷材料。An advantage of the present invention is to provide an electronic device outer cover reinforced nano-membrane and its preparation method and application. In some embodiments, the electronic device outer cover is made of glass or ceramic material.

为了实现以上至少一发明优势，本发明的一方面提供一增强纳米膜，其包括：C、H和一掺杂元素，其以碳氢气体C _xH _y和一掺杂气体作为反应气体原料，通过PECVD工艺在一基体的表面沉积形成，其中所述掺杂气体提供所述掺杂元素。 In order to achieve at least one of the advantages of the above invention, one aspect of the present invention provides an enhanced nanomembrane, which includes: C, H and a doping element, which uses hydrocarbon gas C _x H _y and a doping gas as raw materials for the reaction gas, It is deposited and formed on the surface of a substrate by a PECVD process, wherein the doping gas provides the doping element.

根据一些实施例所述的增强纳米膜，其中碳氢气体C _xH _y是碳原子数为1-6的烷烃、烯烃、炔烃或者苯中的其中一种或多种。 The reinforced nanomembrane according to some embodiments, wherein the hydrocarbon gas C _x H _y is one or more of alkane, alkene, alkyne or benzene with carbon number of 1-6.

根据一些实施例所述的增强纳米膜，其中所述掺杂元素选自Si、N、F、B中的一种或多种。The reinforced nanomembrane according to some embodiments, wherein the doping element is selected from one or more of Si, N, F, and B.

根据一些实施例所述的增强纳米膜，其中掺杂Si元素的所述掺杂气体原料可以是含硅有机化合物，包括有机直链硅氧烷、环硅氧烷、烷氧基硅烷、含不饱和碳碳双键硅氧烷。According to the reinforced nanomembrane according to some embodiments, the doping gas raw material doped with Si element may be a silicon-containing organic compound, including organic linear siloxane, cyclosiloxane, alkoxysilane, Saturated carbon-carbon double bond siloxane.

根据一些实施例所述的增强纳米膜，其中掺杂N元素的所述掺杂气体原料是N ₂、NO ₂、含氮碳氢化合物。 According to the reinforced nano film according to some embodiments, the doping gas raw material doped with N element is N ₂ , NO ₂ , and nitrogen-containing hydrocarbon.

根据一些实施例所述的增强纳米膜，其中掺杂F元素的所述掺杂气体原料是氟碳气体。According to the reinforced nanomembrane according to some embodiments, the doping gas raw material doped with the F element is a fluorocarbon gas.

根据一些实施例所述的增强纳米膜，其中氟碳气体选自四氟化碳、八氟丙烯、八氟环丁烷中的一种或多种。The reinforced nanomembrane according to some embodiments, wherein the fluorocarbon gas is selected from one or more of carbon tetrafluoride, octafluoropropylene, and octafluorocyclobutane.

根据一些实施例所述的增强纳米膜，其中掺杂B元素的所述掺杂气体原料是常压下沸点低于300℃的硼烷。According to the reinforced nanomembrane according to some embodiments, the doping gas raw material doped with element B is borane with a boiling point lower than 300° C. under normal pressure.

根据一些实施例所述的增强纳米膜，其中硼烷选自戊硼烷、己硼烷中的一种或多种。The reinforced nanomembrane according to some embodiments, wherein the borane is selected from one or more of pentaborane and hexaborane.

根据一些实施例所述的增强纳米膜，其中在进行PECVD工艺时，加入一等离子体源气体，以激活所述反应气体原料的沉积反应。According to the enhanced nano film according to some embodiments, during the PECVD process, a plasma source gas is added to activate the deposition reaction of the reactive gas material.

根据一些实施例所述的增强纳米膜，其中所述等离子体源气体选自惰性气体、 氮气、氟碳气体中的其中一种或多种。The reinforced nanomembrane according to some embodiments, wherein the plasma source gas is selected from one or more of inert gas, nitrogen, and fluorocarbon gas.

根据一些实施例所述的增强纳米膜，其中在进行PECVD工艺时，加入一辅助气体，与所述反应气体原料共同沉积反应，其中所述辅助气体是氢气，以调节所述增强纳米膜中的C-H键含量。According to some embodiments of the reinforced nanomembrane, when the PECVD process is performed, an auxiliary gas is added to co-deposit and react with the reactive gas raw material, wherein the auxiliary gas is hydrogen to adjust the content of the reinforced nanomembrane. CH bond content.

根据一些实施例所述的增强纳米膜，其中所述氢气的含量≤40％。The reinforced nanomembrane according to some embodiments, wherein the content of hydrogen is ≤40%.

根据一些实施例所述的增强纳米膜，其中在进行PECVD工艺时，射频和高压脉冲共同作用沉积形成所述增强纳米膜。According to the reinforced nano film according to some embodiments, during the PECVD process, radio frequency and high voltage pulses are combined to form the reinforced nano film.

根据一些实施例所述的增强纳米膜，其中所述射频功率范围为10～800W，脉冲电源电压-100V～-5000V，脉冲占空比10％～80％。The reinforced nanomembrane according to some embodiments, wherein the radio frequency power range is 10-800W, the pulse power supply voltage is -100V-5000V, and the pulse duty ratio is 10%-80%.

根据一些实施例所述的增强纳米膜，其中所述基体是一电子设备外盖。The reinforced nanomembrane according to some embodiments, wherein the substrate is an electronic device cover.

根据一些实施例所述的增强纳米膜，其中所述电子设备选自于智能手机、平板电脑、电子阅读器、可穿戴设备、电视机、电脑显示屏中的一种。The reinforced nanomembrane according to some embodiments, wherein the electronic device is selected from one of a smart phone, a tablet computer, an e-reader, a wearable device, a television, and a computer display screen.

本发明的另一方面提供一增强纳米膜的制备方法，其以碳氢气体C _xH _y和一掺杂气体作为反应气体原料，通过PECVD装置在一基体的表面沉积形成，其中所述掺杂气体提供一掺杂元素。 Another aspect of the present invention provides a method for preparing a reinforced nano film, which uses hydrocarbon gas C _x H _y and a doping gas as raw materials for reaction gas, and is formed by depositing on the surface of a substrate by a PECVD device, wherein the doping The gas provides a doping element.

根据一些实施例所述的增强纳米膜的制备方法，其中包括步骤：向所述PECVD装置通入一等离子体源气体，以激活所述反应气体原料的沉积反应。According to some embodiments, the method for preparing the reinforced nano film includes the step of passing a plasma source gas into the PECVD device to activate the deposition reaction of the reactive gas raw material.

根据一些实施例所述的增强纳米膜的制备方法，其中所述等离子体源气体选自惰性气体、氮气、氟碳气体中的其中一种或多种。According to the method for preparing the reinforced nanomembrane according to some embodiments, the plasma source gas is selected from one or more of inert gas, nitrogen, and fluorocarbon gas.

根据一些实施例所述的增强纳米膜的制备方法，其中包括步骤：打开所述PECVD装置的一高压脉冲电源，所述等离子体源气体在高压脉冲电场的作用下清洁所述基体表面，并且蚀刻和活化。According to some embodiments, the method for preparing a reinforced nanomembrane includes the steps of: turning on a high-voltage pulse power supply of the PECVD device, the plasma source gas cleans the surface of the substrate under the action of the high-voltage pulse electric field, and etching And activation.

根据一些实施例所述的增强纳米膜的制备方法，其中高压脉冲电源电压-100V～-5000V、占空比1％～90％。According to the method for preparing the reinforced nanomembrane according to some embodiments, the high-voltage pulse power supply voltage is -100V-5000V, and the duty ratio is 1%-90%.

根据一些实施例所述的增强纳米膜的制备方法，其中在进行PECVD工艺时，加入一辅助气体，与所述反应气体原料共同沉积反应，其中所述辅助气体是氢气，以调节所述增强纳米膜中的C-H键含量。According to the preparation method of the reinforced nano film according to some embodiments, an auxiliary gas is added during the PECVD process to co-deposit and react with the reactive gas raw material, wherein the auxiliary gas is hydrogen to adjust the reinforced nano film. The content of CH bonds in the film.

根据一些实施例所述的增强纳米膜的制备方法，其中所述氢气的含量≤40％。According to the method for preparing the reinforced nanomembrane according to some embodiments, the content of the hydrogen is ≤40%.

根据一些实施例所述的增强纳米膜制备方法，其中在进行PECVD工艺时，射频和高压脉冲共同作用沉积形成所述增强纳米膜。According to the method for preparing the reinforced nano film according to some embodiments, when the PECVD process is performed, radio frequency and high voltage pulses are combined to form the reinforced nano film.

根据一些实施例所述的增强纳米膜制备方法，其中所述射频功率范围为10～800W，偏压电源电压-100V～-5000V，脉冲占空比10％～80％。According to the method for preparing an enhanced nanomembrane according to some embodiments, wherein the radio frequency power range is 10-800W, the bias power supply voltage is -100V-5000V, and the pulse duty ratio is 10%-80%.

根据一些实施例所述的增强纳米膜制备方法，其中所述基体是一电子设备外盖。According to the method for preparing the reinforced nanomembrane according to some embodiments, the substrate is an electronic device outer cover.

根据一些实施例所述的增强纳米膜制备方法，其中所述电子设备选自于智能手机、平板电脑、电子阅读器、可穿戴设备、电视机、电脑显示屏中的一种。According to the method for preparing the reinforced nanomembrane according to some embodiments, the electronic device is selected from one of a smart phone, a tablet computer, an e-reader, a wearable device, a television, and a computer display screen.

根据一些实施例所述的增强纳米膜的制备方法，其中碳氢气体C _xH _y是碳原子数为1-6的烷烃、烯烃、炔烃或者苯中的其中一种或多种。 According to the method for preparing the reinforced nanomembrane according to some embodiments, the hydrocarbon gas C _x H _y is one or more of alkane, alkene, alkyne or benzene with a carbon number of 1-6.

根据一些实施例所述的增强纳米膜的制备方法，其中所述掺杂元素选自Si、N、F、B中的一种或多种。According to the method for preparing the reinforced nanomembrane according to some embodiments, the doping element is selected from one or more of Si, N, F, and B.

根据一些实施例所述的增强纳米膜的制备方法，其中掺杂Si元素的所述掺杂气体原料可以是含硅有机化合物，包括有机直链硅氧烷、环硅氧烷、烷氧基硅烷、含不饱和碳碳双键硅氧烷。According to the method for preparing the reinforced nanomembrane according to some embodiments, the doping gas raw material doped with Si element may be a silicon-containing organic compound, including organic linear siloxane, cyclosiloxane, and alkoxysilane , Containing unsaturated carbon-carbon double bond siloxane.

根据一些实施例所述的增强纳米膜的制备方法，其中掺杂N元素的所述掺杂气体原料是N ₂、NO ₂、含氮碳氢化合物。 According to the method for preparing the reinforced nanomembrane according to some embodiments, the doping gas raw material doped with N element is N ₂ , NO ₂ , and nitrogen-containing hydrocarbons.

根据一些实施例所述的增强纳米膜的制备方法，其中掺杂F元素的所述掺杂气体原料是氟碳气体。According to the method for preparing the reinforced nanomembrane according to some embodiments, the doping gas raw material doped with the F element is a fluorocarbon gas.

根据一些实施例所述的增强纳米膜的制备方法，其中氟碳气体选自四氟化碳、八氟丙烯、八氟环丁烷中的一种或多种。According to the method for preparing the reinforced nanomembrane according to some embodiments, the fluorocarbon gas is selected from one or more of carbon tetrafluoride, octafluoropropylene, and octafluorocyclobutane.

根据一些实施例所述的增强纳米膜的制备方法，其中掺杂B元素的所述掺杂气体原料是常压下沸点低于300℃的硼烷。According to the method for preparing the reinforced nanomembrane according to some embodiments, the doping gas raw material doped with element B is borane with a boiling point lower than 300° C. under normal pressure.

根据一些实施例所述的增强纳米膜的制备方法，其中硼烷选自戊硼烷、己硼烷中的一种或多种。According to the method for preparing the reinforced nanomembrane according to some embodiments, the borane is selected from one or more of pentaborane and hexaborane.

本发明的另一方面提供一电子设备，其包括：Another aspect of the present invention provides an electronic device, which includes:

一主体；A subject

一外盖；和An outer cover; and

一所述的增强纳米膜，所述外盖被安装于所述主体背面，所述增强纳米膜通过PECVD工艺沉积于所述外盖的表面。In the reinforced nano film, the outer cover is installed on the back of the main body, and the reinforced nano film is deposited on the surface of the outer cover by a PECVD process.

根据一些实施例所述的电子设备，其中所述外盖具有一边缘，所述增强纳米膜进一步覆盖所述外盖的边缘。The electronic device according to some embodiments, wherein the outer cover has an edge, and the reinforced nano film further covers the edge of the outer cover.

本发明的另一方面提供一电子设备，其包括：Another aspect of the present invention provides an electronic device, which includes:

一主体；A subject

一外盖；和An outer cover; and

一根据所述的方法制备的增强纳米膜，所述外盖被安装于所述主体背面，所述增强纳米膜通过PECVD工艺沉积于所述外盖的表面。A reinforced nano film prepared according to the method, the outer cover is installed on the back of the main body, and the reinforced nano film is deposited on the surface of the outer cover through a PECVD process.

根据一些实施例所述的电子设备，其中所述外盖具有一边缘，所述增强纳米膜进一步覆盖所述显示屏的边缘。The electronic device according to some embodiments, wherein the outer cover has an edge, and the reinforced nano film further covers the edge of the display screen.

本发明的另一方面提供一电子设备外盖表面增强的方法，其中将一电子设备暴露于一包含结构式C _xH _y的反应原料气体和一掺杂气体反应原料气体中进行等离子体增强化学气相沉积以使得增强纳米膜在所述电子设备外盖的表面形成。 Another aspect of the present invention provides a method for enhancing the surface of the outer cover of an electronic device, in which an electronic device is exposed to a _{reactive raw material gas containing a structural formula C x} H _y and a doping gas reactive raw material gas for plasma enhanced chemical vaporization It is deposited so that the reinforced nano film is formed on the surface of the outer cover of the electronic device.

根据一些实施例所述的电子设备外盖表面增强的方法，其中包括步骤：将所述电子设备水平放置沉积形成所述增强纳米膜。According to some embodiments, the method for enhancing the surface of the outer cover of an electronic device includes the step of depositing the electronic device horizontally to form the enhanced nano-film.

根据一些实施例所述的电子设备外盖表面增强的方法，其中包括步骤：将洁净的所述电子设备放置于一PECVD装置的真空反应腔中，进行抽真空使腔体内压力降至0.01Pa以下；和According to some embodiments, the method for enhancing the surface of the outer cover of an electronic device includes the steps of: placing the clean electronic device in a vacuum reaction chamber of a PECVD device, and performing vacuuming to reduce the pressure in the chamber to less than 0.01 Pa ;with

通入等离子体源气体进行表面刻蚀处理，腔体内压力控制在10Pa；The plasma source gas is introduced for surface etching treatment, and the pressure in the cavity is controlled at 10 Pa;

打开高压脉冲电源和射频电源的至少其中一个；Turn on at least one of the high-voltage pulse power supply and the radio frequency power supply;

其中向所述真空反应腔体中引入甲烷、氢气、六甲基环三硅氧烷，以制得含氢类增强纳米膜。Wherein, methane, hydrogen, and hexamethylcyclotrisiloxane are introduced into the vacuum reaction chamber to prepare hydrogen-containing reinforced nano-membrane.

根据一些实施例所述的电子设备外盖表面增强的方法，其中向所述真空反应腔体中引入甲烷、氢气、六甲基环三硅氧烷，气体流量分别为150sccm、100sccm、30sccm，压力控制在8Pa。The method for enhancing the surface of the outer cover of an electronic device according to some embodiments, wherein methane, hydrogen, and hexamethylcyclotrisiloxane are introduced into the vacuum reaction chamber, and the gas flow rate is 150 sccm, 100 sccm, and 30 sccm, respectively. Control at 8Pa.

根据一些实施例所述的电子设备外盖表面增强的方法，其中高压脉冲电源电压-100V～-5000V、占空比1％～90％。According to some embodiments of the method for enhancing the surface of the outer cover of an electronic device, the high-voltage pulse power supply has a voltage of -100V to -5000V and a duty ratio of 1% to 90%.

根据一些实施例所述的电子设备外盖表面增强的方法，其中高压脉冲电源电压为-1000V、占空比50％。According to the method for enhancing the surface of the outer cover of an electronic device according to some embodiments, the high-voltage pulse power supply voltage is -1000V and the duty cycle is 50%.

根据一些实施例所述的电子设备外盖表面增强的方法，其中所述氢气的含量≤40％。According to the method for enhancing the surface of the outer cover of an electronic device according to some embodiments, the content of the hydrogen is ≤40%.

附图说明Description of the drawings

图1是根据本发明的一个实施例的增强纳米膜的制备方法框图。Fig. 1 is a block diagram of a method for preparing a reinforced nanomembrane according to an embodiment of the present invention.

图2是上述实施例的增强纳米膜应用于电子设备外盖的示意图。Fig. 2 is a schematic diagram of the reinforced nano-membrane of the above embodiment applied to the outer cover of an electronic device.

具体实施方式detailed description

以下描述用于揭露本发明以使本领域技术人员能够实现本发明。以下描述中的优选实施例只作为举例，本领域技术人员可以想到其他显而易见的变型。在以下描述中界定的本发明的基本原理可以应用于其他实施方案、变形方案、改进方案、等同方案以及没有背离本发明的精神和范围的其他技术方案。The following description is used to disclose the present invention so that those skilled in the art can implement the present invention. The preferred embodiments in the following description are only examples, and those skilled in the art can think of other obvious variations. The basic principles of the present invention defined in the following description can be applied to other embodiments, modifications, improvements, equivalents, and other technical solutions that do not deviate from the spirit and scope of the present invention.

对“一个实施例”、“实施例”、“示例实施例”、“各种实施例”、“一些实施例”等的引用指示这样的描述本发明的实施例可包括特定特征、结构或特性，但是不是每个实施例必须包括该特征、结构或特性。此外，一些实施例可具有对其它实施例的描述的特征中的一些、全部或没有这样的特征。References to "one embodiment", "embodiments", "exemplary embodiments", "various embodiments", "some embodiments", etc. indicate that such embodiments describing the invention may include specific features, structures, or characteristics , But not every embodiment must include this feature, structure, or characteristic. In addition, some embodiments may have some, all, or none of the described features of other embodiments.

本发明提供一电子设备外盖增强纳米膜及其制备方法和应用，其中所述增强纳米膜通过等离子体增强化学气相沉积(PECVD)工艺化学沉积形成于一基体表面，以改善所述基体材料的表面性能。所述基体优选为电子设备外盖，所述表面性能举例地但限于耐磨性能、耐摔性能、残余应力大小。所述电子设备举例地但限于智能手机、平板电脑、电子阅读器、可穿戴设备、电视机、电脑显示屏。优选地，所述电子设备是智能手机。The present invention provides an electronic device outer cover reinforced nano film and a preparation method and application thereof, wherein the reinforced nano film is chemically deposited on a substrate surface through a plasma enhanced chemical vapor deposition (PECVD) process to improve the performance of the substrate material Surface properties. The substrate is preferably an outer cover of an electronic device, and the surface properties are exemplified but limited to wear resistance, drop resistance, and residual stress. The electronic device is exemplified but limited to a smart phone, a tablet computer, an e-reader, a wearable device, a television, and a computer display screen. Preferably, the electronic device is a smart phone.

所述增强纳米膜能够提高所述电子设备屏的耐摔性能，如耐摔次数，在一些实施例中，所述增强纳米膜能够使得耐摔次数较低的所述电子设备外盖的耐摔次数由5次提高至11以及以上，举例地，所述增强纳米膜能够使得所述电子设备屏的耐摔次数提升至11、12、13、14、15、18、19。The reinforced nano film can improve the drop resistance of the electronic device screen, such as the number of times of drop resistance. In some embodiments, the reinforced nano film can make the outer cover of the electronic device with a lower number of drop resistance to withstand the drop. The number of times is increased from 5 times to 11 or more. For example, the reinforced nano-film can increase the number of times of drop resistance of the electronic device screen to 11, 12, 13, 14, 15, 18, and 19.

所述增强纳米膜能够提高所述电子设备外盖的耐摩擦性能，如耐摩擦次数，在一些实施例中，所述增强纳米膜能够使得所述电子设备外盖的耐摩擦次数达42000、48000、31000、51000、53000、55000、56000、65000。The reinforced nano film can improve the friction resistance of the electronic device outer cover, such as the number of friction resistance. In some embodiments, the enhanced nano film can make the electronic device outer cover have a friction resistance of 42,000 and 48,000. , 31000, 51000, 53000, 55000, 56000, 65000.

所述增强纳米膜是纳米尺寸膜，具有较小的厚度，其厚度范围举例地但不限于10～2000nm，在一些实施例中，所述增强纳米膜的厚度分别是22nm、27nm、38nm、42nm、47nm、49nm、54nm、98nm、106nm。The enhanced nano-membrane is a nano-sized film with a relatively small thickness. The thickness range is exemplified but not limited to 10 to 2000 nm. In some embodiments, the thickness of the enhanced nano-membrane is 22 nm, 27 nm, 38 nm, and 42 nm, respectively. , 47nm, 49nm, 54nm, 98nm, 106nm.

所述增强纳米膜采用PECVD工艺气相沉积于所述电子设备外盖的表面，藉由离子态的反应过程，可以使得所述增强纳米膜的厚度较小，如纳米尺寸，且在 PECVD沉积过程可以通过控制工艺参数来获取目标性的所述增强纳米膜，比如，控制获取预定厚度的所述增强纳米膜。也就是说，上述预定厚度的所述增强纳米膜分别是在不同的预定反应条件下获得，而不是任意数值的选取。The enhanced nano-film is vapor-deposited on the surface of the electronic device cover using a PECVD process, and the thickness of the enhanced nano-film can be made smaller, such as nanometer size, through the reaction process of the ion state, and it can be deposited in the PECVD process. The targeted enhanced nano-membrane is obtained by controlling the process parameters, for example, the enhanced nano-membrane with a predetermined thickness is controlled to be obtained. That is to say, the reinforced nano-membrane with the predetermined thickness mentioned above is obtained under different predetermined reaction conditions, rather than arbitrary numerical selection.

所述增强纳米膜能够降低所述电子设备外盖的残余应力，在一些实施例中，带有所述增强纳米膜的所述电子设备外盖的残余应力分别是1.1Gpa、1.5Gpa、1.8Gpa、1.9Gpa、2.1Gpa、3.1Gpa、3.7Gpa、3.8Gpa、7.9Gpa。The reinforced nanomembrane can reduce the residual stress of the outer cover of the electronic device. In some embodiments, the residual stress of the outer cover of the electronic device with the reinforced nanomembrane is 1.1 Gpa, 1.5 Gpa, and 1.8 Gpa, respectively. , 1.9Gpa, 2.1Gpa, 3.1Gpa, 3.7Gpa, 3.8Gpa, 7.9Gpa.

所述增强纳米膜以碳氢气体C _xH _y作为沉积反应气体原料，通过PECVD工艺沉积于所述电子设备外盖表面形成。C _xH _y是1-6碳原子数的烷烃、烯烃、炔烃或者苯。所述反应气体原料可以是单一气体，也可以是两种或者两种以上的气体混合物。 The reinforced nano film is formed by using hydrocarbon gas C _x H _y as a deposition reaction gas raw material and depositing on the surface of the outer cover of the electronic device through a PECVD process. C _x H _y is an alkane, alkene, alkyne or benzene with a carbon number of 1 to 6. The reaction gas raw material can be a single gas or a mixture of two or more gases.

值得一体的是，根据本发明的实施例，由碳氢气体C _xH _y作为沉积反应气体原料通过PECVD工艺制备得到类金刚石薄膜(Diamond Like Carbon，DLC)，其是一种以sp3(金刚石键)和sp2(石墨键)键的形式结合生成的亚稳态材料，是一种短程有序、长程无序的薄膜。它兼具了金刚石和石墨的优良特性。在力学性能方面，具有较高的硬度和较好的耐磨性，与组分相关的硬度可从20GPa变化至80GPa；在光学性能方面，透光性好、有增透功能；还具有良好的导热性和生物相容性。 It is worthwhile to integrate that, according to the embodiment of the present invention, a _{diamond like carbon (DLC) film (Diamond Like Carbon, DLC) is prepared by using a hydrocarbon gas C x} H _y as a deposition reaction gas raw material through a PECVD process, which is a kind of sp3 (diamond bond ) And sp2 (graphite bond) bond to produce a metastable material, which is a short-range ordered and long-range disordered film. It combines the excellent properties of diamond and graphite. In terms of mechanical properties, it has higher hardness and better wear resistance, and the hardness related to the components can be changed from 20GPa to 80GPa; in terms of optical properties, it has good light transmittance and antireflection function; it also has good Thermal conductivity and biocompatibility.

在所述电子设备外盖等表面镀上一层DLC薄膜，比如玻璃、陶瓷、复合塑料等材料制成的电子设备外盖，可进一步提高玻璃、陶瓷、复合塑料等的耐磨性和硬度，将DLC薄膜沉积到塑料表面，可以起到提高塑料表面耐磨性能和提升硬度的作用。Coating a layer of DLC film on the surface of the electronic device cover, such as the electronic device cover made of glass, ceramic, composite plastic, etc., can further improve the wear resistance and hardness of glass, ceramics, composite plastic, etc. Depositing the DLC film on the plastic surface can improve the wear resistance and hardness of the plastic surface.

等离子体增强化学气相沉积(PECVD)工艺相较于现有的其它沉积工艺具有很多优点：(1)干式成膜不需要使用有机溶剂；(2)等离子体对基体表面的刻蚀作用，使所沉积上的薄膜与基体粘结性好；(3)可以对不规则基体表面均匀沉积镀膜，气相渗透性极强；(4)涂层可设计性好，相比于液相法微米级控制精度，化学气相法可在纳米级尺度进行涂层厚度的控制；(5)涂层结构设计容易，化学气相法使用等离子体激活，对不同材料的复合涂层不需要设计特定的引发剂进行引发，通过输入能量的调控即可将多种原材料复合在一起；(6)致密性好，化学气相沉积法在等离子体引发过程中往往会对多个活性位点进行激活，类似于溶液反应中一个分子上有多个官能团，分子链之间通过多个官能团形成交联结构；(7) 作为一种镀膜处理技术手段，其普适性极好，镀膜的对象、镀膜使用的原材料选择的范围都很广。Compared with other existing deposition processes, the plasma-enhanced chemical vapor deposition (PECVD) process has many advantages: (1) Dry film formation does not require the use of organic solvents; (2) Plasma's etching effect on the substrate surface makes The deposited film has good adhesion to the substrate; (3) The coating can be uniformly deposited on the surface of the irregular substrate, and the gas permeability is extremely strong; (4) The coating can be designed well, compared to the liquid phase method with micron level control Accuracy, the chemical vapor method can control the coating thickness at the nanometer scale; (5) The coating structure is easy to design, the chemical vapor method uses plasma activation, and the composite coating of different materials does not need to design a specific initiator for initiation , Through the control of input energy, multiple raw materials can be compounded together; (6) The density is good, and the chemical vapor deposition method often activates multiple active sites during the plasma initiation process, similar to one in a solution reaction. There are multiple functional groups on the molecule, and the molecular chains form a cross-linked structure through multiple functional groups; (7) As a coating treatment technology, its universality is excellent, and the range of coating objects and raw materials used for coating are all Very wide.

所述等离子体增强化学气相沉积(PECVD)工艺通过辉光放电产生等离子体，放电的方法包括微波放电、射频放电、紫外、电火花放电等。The plasma enhanced chemical vapor deposition (PECVD) process generates plasma through glow discharge, and the discharge method includes microwave discharge, radio frequency discharge, ultraviolet, electric spark discharge, and the like.

进一步，根据本发明的实施例，在制备所述增强纳米膜时，在反应气体原料中加入一掺杂气体原料，以便于在沉积形成的所述增强纳米膜中掺入指定元素。也就是说，加入掺杂气体原料与反应气体原料共同进行PECVD沉积反应，以在DLC膜中掺入C、H之外的其它元素，来改变所述DLC膜的性能。Further, according to an embodiment of the present invention, when the reinforced nano film is prepared, a doping gas raw material is added to the reactive gas raw material, so that a specified element can be doped into the reinforced nano film formed by deposition. That is to say, the dopant gas raw material and the reactive gas raw material are added to perform the PECVD deposition reaction together, so that other elements other than C and H are added to the DLC film to change the performance of the DLC film.

所述电子设备外盖加强膜中掺杂的元素举例地但限于Si、N、F、B中的一种或多种，当膜中掺入这些元素时，可降低薄膜的内应力从而提高基体韧性；提高生物相容性；提高表面疏水性能。在一些实施例中，掺杂Si元素的所述掺杂气体原料可以是含硅有机化合物，包括有机直链硅氧烷、环硅氧烷、烷氧基硅烷、含不饱和碳碳双键硅氧烷。在一些实施例中，掺杂N元素的所述掺杂气体原料是N ₂、NO ₂、含氮碳氢化合物。在一些实施例中，掺杂F元素的所述掺杂气体原料是氟碳气体，进一步地，选自四氟化碳、八氟丙烯、八氟环丁烷。在一些实施例中，掺杂B元素的所述掺杂气体原料是常压下沸点低于300℃的硼烷，进一步地，选自戊硼烷、己硼烷。 The elements doped in the reinforcement film for the outer cover of the electronic device are exemplified but limited to one or more of Si, N, F, and B. When these elements are doped in the film, the internal stress of the film can be reduced to increase the matrix. Toughness; improve biocompatibility; improve surface hydrophobicity. In some embodiments, the doping gas raw material doped with Si elements may be silicon-containing organic compounds, including organic linear siloxanes, cyclosiloxanes, alkoxysilanes, and unsaturated carbon-carbon double bond-containing silicon. Oxane. In some embodiments, the doping gas raw material doped with N element is N ₂ , NO ₂ , and nitrogen-containing hydrocarbons. In some embodiments, the doping gas raw material doped with the F element is a fluorocarbon gas, further selected from carbon tetrafluoride, octafluoropropylene, and octafluorocyclobutane. In some embodiments, the doping gas raw material doped with element B is borane with a boiling point lower than 300° C. under normal pressure, and is further selected from pentaborane and hexaborane.

掺杂元素与DLC中的C元素会产生成键作用，破坏原来DLC有序的微观结构，改变沉积过程中结晶生长模式。当含量进一步提高时，可能出现相分离或者完全改变DLC中类金刚石结构，使薄膜丧失了耐磨、高硬度的性能，因此掺杂元素的含量不宜太多。可选地，掺杂的元素含量在DLC薄膜中原子数比例<20％，优选地，掺杂的元素含量在DLC薄膜中原子数比例<10％，在该范围内，可以在不影响DLC薄膜原有的改善性能之外，可以在此基础上改善其它方面的性能，降低薄膜的内应力从而提高基体韧性；提高生物相容性；提高表面疏水性能，比如降低薄膜的内应力从而提高基体韧性；提高生物相容性；提高表面疏水性能。The doping element and the C element in the DLC will form a bond, destroy the orderly microstructure of the original DLC, and change the crystal growth mode during the deposition process. When the content is further increased, phase separation may occur or the diamond-like structure in DLC may be completely changed, causing the film to lose wear resistance and high hardness. Therefore, the content of doped elements should not be too much. Optionally, the content of the doped element in the DLC film is less than 20% of the atomic number. Preferably, the content of the doped element is less than 10% of the atomic number in the DLC film. Within this range, the DLC film may not be affected. In addition to the original improved performance, other aspects of performance can be improved on this basis, reducing the internal stress of the film to improve the toughness of the substrate; improving the biocompatibility; improving the surface hydrophobicity, such as reducing the internal stress of the film to increase the toughness of the substrate ; Improve biocompatibility; Improve surface hydrophobicity.

值得一提的是，掺杂元素的加入，可以使DLC薄膜获得更多的功能运用，但过多的掺杂量可能会破坏原来的碳结构，从而破坏DLC的机械性能，比如氟元素的掺入可以提高膜层疏水效果和透明度，但当氟原子含量超过20％类金刚石涂层的硬度会显著降低，比如低于莫氏硬度4H。It is worth mentioning that the addition of doping elements can make DLC films more functional applications, but too much doping may destroy the original carbon structure, thereby destroying the mechanical properties of DLC, such as the doping of fluorine elements. Inclusion can improve the hydrophobic effect and transparency of the film, but when the content of fluorine atoms exceeds 20%, the hardness of the diamond-like coating will be significantly reduced, for example, lower than the Mohs hardness of 4H.

进一步，根据本发明的一些实施例，在制备所述增强纳米膜时，在PECVD反应装置中通入一等离子体源气体，其用于激活所述反应气体原料的化学沉积反应，预先将基体材料表面进行等离子体适合，以增强所述增强纳米膜与所述基体材料表面的结合力。所述等离子体源气体举例地但限于惰性气体、氮气、氟碳气体，其中惰性气体举例地但不限于He、Ar，氟碳气体举例地但不限于四氟化碳。所述等离子体源气体是可以单一气体，也可以是两种或者两种以上的气体的混合物。所述等离子源气体可以与所述反应气体同时通入，也可以先后通入。优选地，先通入所述等离子体源，而后再通入所述反应气体原料。首先在基体表面进行等离子体刻蚀，然后再沉积DLC薄膜，使DLC涂层与基体粘接性得到很大的增强，强化了基体的表面，能有效抑制Griffith的裂纹的产生。Further, according to some embodiments of the present invention, when preparing the enhanced nanomembrane, a plasma source gas is introduced into the PECVD reaction device, which is used to activate the chemical deposition reaction of the reactive gas raw materials, and the matrix material The surface is subjected to plasma adaptation to enhance the bonding force of the reinforced nano-membrane with the surface of the base material. The plasma source gas is exemplified but not limited to inert gas, nitrogen, fluorocarbon gas, wherein the inert gas is exemplified but not limited to He and Ar, and the fluorocarbon gas is exemplified but not limited to carbon tetrafluoride. The plasma source gas may be a single gas or a mixture of two or more gases. The plasma source gas may be passed in simultaneously with the reaction gas, or may be passed in sequentially. Preferably, the plasma source is first introduced, and then the reaction gas raw material is introduced. Plasma etching is performed on the surface of the substrate first, and then the DLC film is deposited, so that the adhesion of the DLC coating to the substrate is greatly enhanced, the surface of the substrate is strengthened, and the generation of Griffith cracks can be effectively suppressed.

进一步，根据本发明的一些实施例，在制备所述增强纳米膜时，在所述PECVD反应装置中通入一辅助气体，所述辅助气体与所述反应气体原料配合形成所述增强纳米膜。也就是说，其将作为增强纳米膜的组成部分。所述辅助气体用于调节所述增强纳米膜的性能，比如调节刚性提高柔韧性。通过所述辅助气体的添加可以调节单纯碳氢气体形成的所述增强纳米膜中的C-C含量和/或C-H含量，以及结合所述辅助气体自身的特征来调整所述增强纳米膜的性能。Further, according to some embodiments of the present invention, when preparing the reinforced nano film, an auxiliary gas is passed into the PECVD reaction device, and the auxiliary gas cooperates with the reaction gas raw material to form the reinforced nano film. In other words, it will serve as a component of the reinforced nanomembrane. The auxiliary gas is used to adjust the performance of the reinforced nanomembrane, such as adjusting the rigidity and improving the flexibility. The addition of the auxiliary gas can adjust the C-C content and/or C-H content in the enhanced nano-film formed by pure hydrocarbon gas, and adjust the performance of the enhanced nano-film in combination with the characteristics of the auxiliary gas itself.

所述辅助气体举例但不限于氢气，所述辅助气体的作用是，所述辅助气体可以与所述反应气体原料同时通入，也可以先后通入，优选地，所述辅助气体与所述反应气体原料同时通入。也就是说，由此可以制得含氢类金刚石薄膜。The auxiliary gas is exemplified but not limited to hydrogen. The function of the auxiliary gas is that the auxiliary gas can be passed in at the same time as the raw material of the reaction gas, or it can be passed in successively. Preferably, the auxiliary gas and the reaction gas Gas raw materials are introduced at the same time. In other words, a hydrogen-containing diamond-like carbon thin film can be produced thereby.

值得一提的是，所述辅助气体的加入能够调节所述增强纳米膜的性能，其在增加改善性能同时会相对弱化所述增强纳米膜的刚性以及原本的性能，因此需要平衡添加量。发明人发现，当加入所述辅助气体时，可以改善所述增强纳米膜的预定性能，但是当所述辅助气体的加入量增加到一定程度时，所述增强纳米膜的硬度会明显下降。比如，当所述辅助气体是氢气时，当氢气含量大于40％时，其刚性会明显下降。含氢DLC相较于无氢DLC有着更高的润滑性和透明性，少量氢有利于SP3键的形成，在一定程度上可以提高硬度，但随着氢含量的进一步提高，类金刚石薄膜的硬度会逐步下降。It is worth mentioning that the addition of the auxiliary gas can adjust the performance of the enhanced nanomembrane, which increases and improves the performance while relatively weakening the rigidity and original performance of the enhanced nanomembrane. Therefore, it is necessary to balance the added amount. The inventor found that when the auxiliary gas is added, the predetermined performance of the reinforced nanomembrane can be improved, but when the added amount of the auxiliary gas is increased to a certain extent, the hardness of the reinforced nanomembrane will be significantly reduced. For example, when the auxiliary gas is hydrogen, when the hydrogen content is greater than 40%, its rigidity will be significantly reduced. Compared with hydrogen-free DLC, hydrogen-containing DLC has higher lubricity and transparency. A small amount of hydrogen is conducive to the formation of SP3 bonds, which can increase the hardness to a certain extent, but with the further increase of hydrogen content, the hardness of the diamond-like carbon film Will gradually decline.

还值得一提的是，所述辅助气体的加入不仅能够调整所述增强纳米膜的性能，其还能够增加PECVD反应过程的离化浓度，促使反应更加快速地进行。It is also worth mentioning that the addition of the auxiliary gas can not only adjust the performance of the enhanced nanomembrane, it can also increase the ionization concentration of the PECVD reaction process, and promote the reaction to proceed more quickly.

进一步，根据本发明的实施例，在制备所述增强纳米膜时，采用射频和高压 脉冲的共同作用来辅助完成等离子体增强化学气相沉积过程。优选地，射频和高压脉冲同时作用于PECVD沉积过程。在射频和高压脉冲共同作用的过程中，利用低功率射频放电维持等离子体环境，抑制高压放电过程的弧光放电，由此提高化学沉积效率。弧光放电是辉光放电进一步加强的放电形式，其瞬间电流可以达到几十甚至几百安培以上，这些高电流经过产品表面损坏产品，由于对于电子产品，其危害更大，而低频率射频放电维持低温等离子体环境，由此抑制脉冲高压放电过程的弧光放电，射频电场和脉冲电场相互配合来优化沉积过程，减少对待沉积的基体的损伤。Further, according to an embodiment of the present invention, when preparing the enhanced nano-membrane, the combined action of radio frequency and high voltage pulse is used to assist in completing the plasma enhanced chemical vapor deposition process. Preferably, radio frequency and high voltage pulses are applied to the PECVD deposition process at the same time. In the process of the combined action of radio frequency and high-voltage pulses, low-power radio-frequency discharge is used to maintain the plasma environment and suppress arc discharge in the high-voltage discharge process, thereby improving the efficiency of chemical deposition. Arc discharge is a form of discharge that is further enhanced by glow discharge. Its instantaneous current can reach tens or even hundreds of amperes or more. These high currents pass through the surface of the product and damage the product. Because it is more harmful to electronic products, low-frequency radio frequency discharge maintains The low-temperature plasma environment suppresses the arc discharge in the pulsed high-voltage discharge process. The radio frequency electric field and the pulsed electric field cooperate with each other to optimize the deposition process and reduce the damage to the substrate to be deposited.

射频可通过对惰性气体、反应气体原料的放电使整个镀膜过程处于等离子体环境，反应气体原料处于高能量状态；脉冲高电压的作用是脉冲电源在放电过程中产生强电场，处于高能状态的活性粒子受到强电场作用加速沉积于基体表面，形成非晶态碳网络结构。脉冲电源处于不放电的状态时，利于沉积在基体表面的DLC薄膜进行非晶态碳网络结构自由驰豫，在热力学作用下碳结构向稳定相---弯曲石墨烯片层结构转变，并埋置于非晶碳网络中，形成透明类石墨烯结构。也就是说，射频电场、变化的脉冲电场相互结合作用，使得所述增强纳米膜能够快速、稳定地沉积于基体的表面。Radio frequency can make the entire coating process in a plasma environment by discharging inert gas and reactive gas raw materials, and the reactive gas raw materials are in a high-energy state; the function of pulsed high voltage is that the pulsed power supply generates a strong electric field during the discharge process and is active in a high-energy state The particles are accelerated to deposit on the surface of the substrate under the action of a strong electric field, forming an amorphous carbon network structure. When the pulse power supply is in a non-discharge state, it is beneficial for the DLC film deposited on the surface of the substrate to freely relax the amorphous carbon network structure. Under the action of thermodynamics, the carbon structure transforms to the stable phase---the curved graphene sheet structure, and is buried Placed in the amorphous carbon network to form a transparent graphene-like structure. In other words, the combination of the radio frequency electric field and the varying pulsed electric field enables the enhanced nano-film to be deposited on the surface of the substrate quickly and stably.

在本发明的一个实施例中，把射频电源作为ICP(电感耦合)离子源的电源供应，通过线圈的电感耦合作用，产生交变磁场，从而实现气体电离，所用射频功率为13.56MHz，快速变化的磁场确保了电离的充分和均匀。脉冲偏压电源加载在阴极上，通过辉光放电效应电离气体，同时对正离子有定向牵引加速作用，在膜层沉积过程有轰击效果，从而可以获得致密的高硬度镀层。同时使用射频ICP源和脉冲偏压电源，在获得了高离化率的等离子体基础上，增加了等离子体到达基体表面时的能量，以获得致密透明的类金刚石薄膜。In an embodiment of the present invention, the radio frequency power is used as the power supply of the ICP (inductive coupling) ion source, and the alternating magnetic field is generated through the inductive coupling of the coil, thereby realizing gas ionization. The radio frequency power used is 13.56 MHz, which changes rapidly. The magnetic field ensures sufficient and uniform ionization. The pulse bias power supply is loaded on the cathode to ionize the gas through the glow discharge effect, and at the same time has the directional pulling and accelerating effect on the positive ions, and has the bombardment effect in the film deposition process, so that a dense and high-hardness coating can be obtained. At the same time, the radio frequency ICP source and the pulse bias power supply are used to obtain a plasma with a high ionization rate and increase the energy when the plasma reaches the surface of the substrate to obtain a dense and transparent diamond-like carbon film.

值得一提的是，射频和高压脉冲的共同作用增强了沉积效率，使得在电子设备屏幕表面能够有效沉积形成保护膜，也就是说，在较短时间内化学沉积反应形成所述增强纳米膜，由此提高了生产效率，使得所述增强纳米膜能够被批量化的工业生产。It is worth mentioning that the combined action of radio frequency and high-voltage pulses enhances the deposition efficiency, so that the protective film can be effectively deposited on the surface of the electronic device screen, that is, the chemical deposition reaction forms the enhanced nano-film in a relatively short time. As a result, the production efficiency is improved, so that the reinforced nano-membrane can be mass-produced industrially.

还值得一提的是，在现有技术中，通常采用磁控溅射镀膜的方式来形成类金刚石薄膜DLC，磁控溅射工艺是PVD工艺的一种，其以碳源作为块状石墨靶材，其离化效率和沉积效率都较低，因此并没有被广泛应用，也比较难应用于大规模 的生产实践当中。而在本发明的实施例中，PECVD碳源为气体，通过外加的直流脉冲和射频电源进行电离作用，离化程度和沉积效率提高，能够形成高硬度的DLC膜层，同时成本更低。DLC薄膜可以使用物理气相沉积法也可以采用化学气相沉积法，相比于化学气相沉积法，物理气相沉积法的设备复杂、价格较高，大面积镀膜比较困难。另一方面，在PVD工艺中，以石墨作为碳源靶材，在制备过程中，需要对其预先加热，且反应速率慢，因此在整个过程中的热量积累较多，反应温度较高。而在本发明的PECVD反应过程中，碳源是气体，其不需要加热过程，沉积的薄膜较薄，沉积时间较短，因此在整个过程中的热量积累较少，反应温度较低，可以控制在25℃～100℃，适于一些电子设备的镀膜。It is also worth mentioning that in the prior art, the diamond-like carbon film DLC is usually formed by magnetron sputtering coating. The magnetron sputtering process is a kind of PVD process, which uses a carbon source as a bulk graphite target. The material, its ionization efficiency and deposition efficiency are low, so it has not been widely used, and it is more difficult to apply to large-scale production practice. In the embodiment of the present invention, the PECVD carbon source is a gas, and the ionization is performed by an external DC pulse and a radio frequency power supply. The ionization degree and the deposition efficiency are improved, and a high-hardness DLC film can be formed at a lower cost. DLC film can use physical vapor deposition method or chemical vapor deposition method. Compared with chemical vapor deposition method, physical vapor deposition method has complicated equipment and higher price, and it is difficult to coat large area. On the other hand, in the PVD process, graphite is used as the carbon source target. During the preparation process, it needs to be pre-heated and the reaction rate is slow. Therefore, the heat accumulation in the whole process is more and the reaction temperature is higher. In the PECVD reaction process of the present invention, the carbon source is a gas, which does not require a heating process, the deposited film is thinner, and the deposition time is shorter. Therefore, the heat accumulation in the whole process is less, the reaction temperature is lower, and it can be controlled. At 25℃～100℃, it is suitable for coating some electronic equipment.

还值得一提的是，在实际的工业生产中，生产效率是其中一个重要因素，以手机屏幕为例，其只是手机众多部件中的其中一个，如果单纯为了提高外盖的一些性能而耗费大量的时间，这个对于实际生产应用是不可行的，比如，在现有的一些DLC膜中，虽然其能够通过较长的反应时间达到改善性能的效果，但是其并不适于批量的生产应用，这也是限制一些膜被实际应用的一个因素之一，而在本发明的实施例中，通过PECVD的化学沉积方式，其能够通过相对简单的工艺过程，通过射频和高压脉冲的共同作用，使得沉积速率有效提高，由此使得外盖增强纳米膜能够被广泛应用于批量化的工业生产中。It is also worth mentioning that in actual industrial production, production efficiency is one of the important factors. Taking the mobile phone screen as an example, it is only one of the many parts of the mobile phone. If it is purely to improve some performance of the outer cover, it will cost a lot of money. This is not feasible for actual production applications. For example, in some existing DLC films, although they can achieve the effect of improving performance through a longer reaction time, they are not suitable for mass production applications. It is also one of the factors that limit the practical application of some films. In the embodiment of the present invention, through the chemical deposition method of PECVD, it can achieve the deposition rate through a relatively simple process through the combined action of radio frequency and high voltage pulses. Effectively improve, thereby enabling the outer cover reinforced nano-membrane to be widely used in mass industrial production.

根据本发明的上述实施例，提供一增强纳米膜的制备方法，其包括如下步骤：According to the above-mentioned embodiment of the present invention, a method for preparing a reinforced nanomembrane is provided, which includes the following steps:

(A)放置一基体于一PECVD反应腔室内；(A) Place a substrate in a PECVD reaction chamber;

(B)将等离子体源气体通入到反应腔室中；(B) Pass the plasma source gas into the reaction chamber;

(C)将包括有碳氢气体的反应气体原料、掺杂气体原料与辅助气体的气体混合物流入到反应腔室中；(C) Flowing a gas mixture of reactive gas raw materials including hydrocarbon gas, dopant gas raw materials, and auxiliary gas into the reaction chamber;

(D)打开射频电源和/或高压脉冲电源，沉积掺杂元素的DLC薄膜；和(D) Turn on the RF power supply and/or the high-voltage pulse power supply, and deposit the element-doped DLC film; and

(E)通入空气或者惰性气体取出基体。(E) Pass in air or inert gas to take out the substrate.

在所述步骤(B)中，所述步骤(B)中的气体可以和步骤(C)中的气体同时通入，也可以先后通入，也可以不通入所述等离子体源气体。当通入所述等离子体源气体时，在一些情况下，所述反应腔室中的气体浓度或者说等离子体的浓度升高，相互激发作用增强，在一定程度上反应速率会提高，以及改善沉积效果。In the step (B), the gas in the step (B) may be passed in at the same time as the gas in the step (C), or may be passed in sequentially, or the plasma source gas may not be passed in. When the plasma source gas is introduced, in some cases, the gas concentration or plasma concentration in the reaction chamber increases, the mutual excitation effect is enhanced, and the reaction rate will increase to a certain extent, and improve Deposition effect.

在所述步骤(C)中，所述反应气体原料可以和所述掺杂气体、所述辅助气 体同时通入，也可以先后通入，也可以不通入所述辅助气体。当通入所述辅助气体时，由碳氢气体和辅助气体共同反应沉积形成所述增强纳米膜，此时的增强纳米膜的性能相对于加入所述辅助气体的增强纳米膜，在一些性能上存在差异，比如刚性减小，具有较好的柔韧性、疏水性、润滑性、透明性等，所述掺杂气体基于掺杂元素的性能改善所述DLC薄膜的相应性能。In the step (C), the reaction gas raw material may be passed in at the same time as the doping gas and the auxiliary gas, or may be passed in successively, or the auxiliary gas may not be passed in. When the auxiliary gas is introduced, the enhanced nano-film is formed by the reaction and deposition of hydrocarbon gas and auxiliary gas. The performance of the enhanced nano-film at this time is relative to that of the enhanced nano-film added with the auxiliary gas. There are differences, such as reduced rigidity, better flexibility, hydrophobicity, lubricity, transparency, etc., and the doping gas improves the corresponding performance of the DLC film based on the performance of the doping element.

在所述步骤(D)中，所述射频电源和所述高压脉冲电源可以同时打开，也可以先后打开。在一些实施例中，在所述步骤(B)执行的过程中，先打开所述高压脉冲电源，在所述步骤(C)执行的过程中，再打开所述射频电源，由此使得两个电场先后配合工作。在一些实施例中，在所述步骤(B)执行的过程中，打开所述射频电源，在所述步骤(C)执行的过程中，再打开所述高压脉冲电源，由此使得两个电场先后配合工作。值得一提的是，在这两种方式中，高压脉冲电场相对属于高能电能，而射频电源相对属于低能电场，因此在所述步骤(B)执行的过程中，即通入所述等离子体源气体时，打开所述高压脉冲电场，使得高能电场为所述等离子体源气体提供充分地离化和清洗的能量，使得离化率更高，更有助于后期的沉积反应，因此整体的沉积反应效果更好。如果在是所述步骤(B)执行的过程中，即通入所述等离子体源气体时，打开所述射频电场，其能量较低，离化作用较弱，对于后期的沉积反应激活作用减弱，因此整体的薄膜沉积效果较差。In the step (D), the radio frequency power supply and the high-voltage pulse power supply may be turned on simultaneously or sequentially. In some embodiments, during the execution of step (B), the high-voltage pulse power supply is first turned on, and during the execution of step (C), the radio frequency power supply is turned on, so that two The electric field works in succession. In some embodiments, during the execution of step (B), the radio frequency power supply is turned on, and during the execution of step (C), the high-voltage pulse power supply is turned on again, so that the two electric fields Cooperate with the work successively. It is worth mentioning that in these two methods, the high-voltage pulsed electric field is relatively high-energy electric energy, while the radio frequency power supply is relatively low-energy electric field. Therefore, during the execution of step (B), the plasma source When gas, the high-voltage pulse electric field is turned on, so that the high-energy electric field provides sufficient energy for ionization and cleaning of the plasma source gas, so that the ionization rate is higher, and it is more helpful for the later deposition reaction, so the overall deposition The response is better. If the radio frequency electric field is turned on during the execution of the step (B), that is, when the plasma source gas is introduced, the energy of the radio frequency electric field is lower, the ionization effect is weak, and the activation effect for the later deposition reaction is weakened , So the overall film deposition effect is poor.

在一些实施例中，所述射频电源和所述高压脉冲电源也可以同时打开，但是相对于先后打开的作用，这种情况下更耗能。在步骤(B)中由于单独的等离子体源气体并不需要直接沉积成薄膜，因此也不需要沉积的能量，两个电场的同时加入就会提供过多的能量，由此使得能源浪费，且在一定程度上，会引起对所述基体的过度蚀刻，另一方面，由于在所述步骤(C)中，通入碳氢气体需要沉积形成薄膜，因此不仅需要离化的能量，也需要迁移沉积到基体表面的能量，而单独过高的脉冲电压不易控制且可能损害基体，因此射频电场和高压脉冲电场配合来提供沉积所需的整体能量，使得沉积过程能够快速、稳定地进行。因此总体来说，所述射频电场和所述高压脉冲电场先后配合的方式薄膜沉积效果优于同时作用或者单独一个作用的效果。In some embodiments, the radio frequency power supply and the high-voltage pulse power supply can also be turned on at the same time, but compared to the effect of turning on sequentially, this situation consumes more energy. In step (B), since the separate plasma source gas does not need to be directly deposited into a thin film, so there is no need for energy for deposition. The simultaneous addition of two electric fields will provide too much energy, thereby making energy waste and To a certain extent, it will cause excessive etching of the substrate. On the other hand, because in the step (C), the hydrocarbon gas needs to be deposited to form a thin film, so not only the energy for ionization, but also the migration is required. The energy deposited on the surface of the substrate is difficult to control and may damage the substrate if the pulse voltage is too high alone. Therefore, the radio frequency electric field and the high-voltage pulsed electric field cooperate to provide the overall energy required for the deposition, so that the deposition process can be carried out quickly and stably. Therefore, in general, the film deposition effect of the combination of the radio frequency electric field and the high-voltage pulsed electric field is better than the effect of simultaneous action or a single action.

具体地，所述增强纳米膜的制备方法可以包括如下过程：Specifically, the preparation method of the reinforced nanomembrane may include the following processes:

(1)基体表面清洁预处理。将玻璃、金属、塑料等基体用酒精或者丙酮等 溶剂进行表面清洗，再用无尘布擦拭或者先经过超声浸泡后擦干；将基体放置于真空反应腔中，抽真空至10Pa以下，更佳地应该抽真空至0.1Pa以下，通入高纯氦气或者氩气作为等离子体气源，打开高压脉冲电源，辉光放电产生等离子体，对样品表面进行刻蚀与活化。即，上述步骤(A)和(B)的一个实施过程。(1) Cleaning and pretreatment of the substrate surface. Clean the surface of glass, metal, plastic and other substrates with alcohol or acetone and other solvents, and then wipe them with a dust-free cloth or first ultrasonic soaking and then wipe them dry; place the substrate in a vacuum reaction chamber and vacuum to below 10Pa, better The ground should be evacuated to below 0.1Pa, and high-purity helium or argon gas should be introduced as the plasma gas source, the high-voltage pulse power supply is turned on, and the glow discharge generates plasma to etch and activate the sample surface. That is, an implementation process of the above steps (A) and (B).

(2)沉积DLC薄膜。利用射频与高压脉冲共同辅助等离子体化学气相沉积的方法制备掺杂类金刚石碳膜：通入DLC薄膜反应气体源、掺杂元素的反应气体原料、氢气，打开射频电源和高压脉冲电源进行等离子体化学气相沉积，经过一段时间后，沉积薄膜过程结束，通入空气或者惰性气体取出样品。即，上述步骤(C)-(E)的一个实施过程。(2) Deposit DLC thin film. Preparation of doped diamond-like carbon film by using radio frequency and high-voltage pulses to assist plasma chemical vapor deposition: pass in DLC film reactive gas source, doped reactive gas raw materials, and hydrogen, turn on the RF power supply and high-voltage pulse power supply for plasma In chemical vapor deposition, after a period of time, the film deposition process ends, and the sample is taken out by introducing air or inert gas. That is, an implementation process of the above steps (C)-(E).

步骤(1)是基体样品表面清洗与活化阶段，通入氩气或者氦气或者四氟化碳的流量为10sccm～1000sccm，控制反应腔中的压力为1～100Pa，打开高压脉冲电源，电压-100V～-5000V、占空比1％～90％，等离子清洗与活化持续时间为1～60min。Step (1) is the cleaning and activation stage of the substrate sample surface. The flow of argon or helium or carbon tetrafluoride is 10sccm～1000sccm, the pressure in the reaction chamber is controlled to 1～100Pa, the high voltage pulse power supply is turned on, and the voltage is- 100V～-5000V, duty ratio 1%～90%, plasma cleaning and activation duration is 1～60min.

在一个实施例中的步骤(1)中，只需要高压脉冲电场的作用来对所述基体的表面进行预处理，而不需要射频电场和高压脉冲电场的共同作用。举例地，在步骤(1)中，所述等离子体源气体，如氩气或者氦气，在高压脉冲电场的作用下产生等离子体，并且在基体表面进行等离子体气相沉积过程，其对基体的表面进行微量蚀刻，即剥离微量的表层，但是由于其惰性作用，其并不能沉积停留于所述基体的表面。也就是说，在该过程中，主要是对表面的部分清除，而没有形成沉积层。步骤(1)为所述反应气体原料的沉积准备离化条件，并且使得基体的表面被微量的蚀刻，清洗表面，使得后续沉积的增强纳米膜更加牢固地结合于基体的表面。In step (1) in one embodiment, only the action of the high-voltage pulsed electric field is required to pre-treat the surface of the substrate, and the combined action of the radio frequency electric field and the high-voltage pulsed electric field is not required. For example, in step (1), the plasma source gas, such as argon or helium, generates plasma under the action of a high-voltage pulsed electric field, and a plasma vapor deposition process is performed on the surface of the substrate. The surface is micro-etched, that is, a small amount of surface layer is peeled off, but due to its inert effect, it cannot deposit and stay on the surface of the substrate. That is to say, in this process, part of the surface is mainly removed without forming a deposited layer. Step (1) prepares ionization conditions for the deposition of the reactive gas raw materials, and causes the surface of the substrate to be slightly etched to clean the surface, so that the subsequently deposited reinforced nano film is more firmly bonded to the surface of the substrate.

值得一提的是，加入反应装置的气体流量对应相应的压力大小，过高或者过低的压力都会影响离化效果。过低的压力达不到清洗效果，过高的压力会存在损坏基体的风险。清洗时间长短影响清洗效果，清洗时间太短达不到清洗效果，清洗时间太长，会有过度蚀刻的风险，且会使得整个工艺周期增长，提高工艺成本。根据本发明的实施例，在通入所述等离子体源的阶段，通入氩气或者氦气的流量10sccm～1000sccm，控制反应腔中的压力为1～100Pa，高压脉冲电源电压-100V～-5000V、占空比1％～90％、清洗时间1～60min，在这些范围，可以较好地调节上述各种因素，使其有利于整个所述增强纳米膜的沉积过程。It is worth mentioning that the gas flow rate added to the reaction device corresponds to the corresponding pressure, too high or too low pressure will affect the ionization effect. Too low pressure cannot achieve the cleaning effect, and too high pressure may damage the substrate. The length of the cleaning time affects the cleaning effect, and the cleaning time is too short to achieve the cleaning effect. If the cleaning time is too long, there will be a risk of over-etching, and it will increase the entire process cycle and increase the process cost. According to an embodiment of the present invention, at the stage of introducing the plasma source, the flow rate of argon or helium is 10sccm～1000sccm, the pressure in the reaction chamber is controlled to be 1～100Pa, and the high voltage pulse power supply voltage is -100V～- 5000V, a duty ratio of 1% to 90%, and a cleaning time of 1 to 60 minutes. Within these ranges, the above-mentioned various factors can be better adjusted to facilitate the entire deposition process of the enhanced nano-film.

在步骤(2)中，采用射频和高压脉冲辅助等离子体化学气相沉积的方法制备掺杂元素的类金刚石碳膜。射频可通过对惰性气体、反应气体原料的放电使整个镀膜过程处于等离子体环境，反应气体原料处于高能量状态；在基体底部施加脉冲高电压，优势是脉冲电源在放电过程中产生强电场，处于高能状态的活性粒子受到强电场作用加速沉积于基体表面。此外，高的偏压电场还有助于掺杂元素与类金刚石薄膜中碳元素的成键作用，提高涂层的致密性。In step (2), the element-doped diamond-like carbon film is prepared by the method of radio frequency and high-voltage pulse-assisted plasma chemical vapor deposition. Radio frequency can make the entire coating process in a plasma environment by discharging inert gas and reactive gas raw materials, and the reactive gas raw materials are in a high-energy state; pulse high voltage is applied to the bottom of the substrate. The advantage is that the pulse power generates a strong electric field during the discharge process. The active particles in the high-energy state are accelerated by the action of the strong electric field to deposit on the surface of the substrate. In addition, the high bias voltage field also contributes to the bonding of doped elements and carbon elements in the diamond-like carbon film, and improves the compactness of the coating.

在沉积过程中，通入一定惰性气体，比如氩气、氦气，可被电场激发出大量的电子、正离子，提高反应腔体中等离子体的密度。这些等离子体会将其本身携带的能量传递给反应气体原料。惰性气体流量一般控制在10-200sccm。而通入H ₂会与C源发生C-H成键反应，C-H键的存在使DLC膜层的柔韧性得到提高，但如果在DLC沉积过程中H含量过高，比如超过40％，则会降低DLC涂层的硬度。控制H ₂与DLC沉积的碳氢有机化合物的流量比例小于2，并且根据碳氢有机化合物中氢含量的大小，调整进气的流量比。值得一提的是，DLC碳源来自烷烃，那么氢气的流量就要小一些；碳源来自炔烃、多烯烃，则氢气流量比例可以提高。在500L的反应腔体中，氢气气体流量控制在0～200sccm、真空反应腔压力为0.01Pa～100Pa，射频功率范围为10～800W，偏压电源电压-100V～-5000V，占空比10％～80％。真空反应腔进一步增大，单炉处理样品量增加，则可以相应地提高DLC碳源气体、氢气、掺杂元素的反应原料流量，通过控制反应原料的原料和镀膜时间还可以控制掺杂的DLC纳米涂层的厚度。 During the deposition process, a certain inert gas, such as argon and helium, can be excited by the electric field to generate a large number of electrons and positive ions, thereby increasing the plasma density in the reaction chamber. These plasmas transfer their own energy to the reactant gas materials. The flow of inert gas is generally controlled at 10-200sccm. The introduction of H ₂ will cause a CH bond reaction with the C source. The presence of CH bonds improves the flexibility of the DLC film. However, if the H content during the DLC deposition process is too high, such as more than 40%, the DLC will be reduced. The hardness of the coating. Control _{the flow ratio of H 2} to the hydrocarbon organic compound deposited by the DLC to be less than 2, and adjust the flow ratio of the intake air according to the hydrogen content of the hydrocarbon organic compound. It is worth mentioning that if the DLC carbon source comes from alkanes, the flow rate of hydrogen will be smaller; if the carbon source comes from alkynes and polyolefins, the proportion of hydrogen flow rate can be increased. In a 500L reaction chamber, the hydrogen gas flow is controlled at 0～200sccm, the vacuum reaction chamber pressure is 0.01Pa～100Pa, the RF power range is 10～800W, the bias power supply voltage is -100V～-5000V, and the duty cycle is 10%. ~80%. The vacuum reaction chamber is further enlarged, and the sample volume processed by a single furnace is increased. The flow rate of the reaction raw materials of DLC carbon source gas, hydrogen, and doping elements can be increased accordingly. The doped DLC can also be controlled by controlling the raw materials of the reaction raw materials and the coating time. The thickness of the nano coating.

惰性气体、氢气在气相沉积过程中对DLC薄膜具有刻蚀作用，流量较大时，比如与碳源气体流量比超过3时，会很大程度上降低薄膜的沉积速度；另外一方面，刻蚀作用能将沉积过程中来不及扩散、松散的薄膜去除，使薄膜更加致密。Inert gas and hydrogen have an etching effect on the DLC film during the vapor deposition process. When the flow rate is large, for example, when the flow rate of the carbon source gas exceeds 3, the deposition rate of the film will be greatly reduced; on the other hand, etching The function can remove the film that is too late to diffuse and loose during the deposition process, making the film more dense.

在所述反应气体原料沉积的阶段，通入的不同气体流量比影响所述增强纳米膜的原子比例，影响膜层的性能，根据本发明的实施例，当C _xH _y流量为50-1000sccm、惰性气体流量10～200sccm、H ₂的气体流量0～100sccm时，所述增强纳米膜的刚性较好，且可以通过氢气调节所述增强纳米膜的柔韧性，并且保持预定的沉积反应速率。 During the deposition of the reactive gas raw materials, the ratio of the different gas flow rates introduced affects the atomic ratio of the reinforced nanomembrane and affects the performance of the membrane layer. According to the embodiment of the present invention, when the C _x H _y flow rate is 50-1000 sccm When the inert gas flow rate is 10 to 200 sccm and the H ₂ gas flow rate is 0 to 100 sccm, the rigidity of the enhanced nanomembrane is better, and the flexibility of the enhanced nanomembrane can be adjusted by hydrogen, and the predetermined deposition reaction rate can be maintained.

在所述反应气体原料沉积的阶段，射频电场和脉冲电场的电源功率的大小影响电离过程的升温、离化率和沉积速率等相关参数，根据本发明的实施例，当射频功率10～800W，偏压电源电压-100V～-5000V、脉冲占空比10％～80％，在这些 参数范围时，可以使得温升不会过快，也不会过度延长工艺时间，使得离化率较高并且保持较好的沉积速率。During the deposition of the reactive gas materials, the magnitude of the power of the radio frequency electric field and the power of the pulsed electric field affects the temperature rise, ionization rate, deposition rate and other related parameters of the ionization process. According to the embodiment of the present invention, when the radio frequency power is 10 to 800 W, The bias power supply voltage is -100V～-5000V, and the pulse duty ratio is 10%～80%. When these parameters are in the range, the temperature rise will not be too fast, and the process time will not be excessively prolonged, making the ionization rate high and Maintain a good deposition rate.

负偏压值的大小直接关系到气体离化情况和到达产品表面时的迁移能力。高电压意味着更高的能量，可以获得高硬度涂层。但需要注意的时高的离子能量，会对基体产品产生很强的轰击效应，所以在微观尺度上会在表面产生轰击坑，同时高能量轰击会加快温度提升，可能导致温度过高而损坏产品，因此需要在偏压值、反应温度以及反应速率之间平衡。The magnitude of the negative bias value is directly related to the ionization of the gas and the migration ability when it reaches the surface of the product. High voltage means higher energy, and high hardness coatings can be obtained. However, it should be noted that the high ion energy will have a strong bombardment effect on the matrix product, so bombardment pits will be generated on the surface on a microscopic scale. At the same time, high-energy bombardment will accelerate the temperature rise, which may cause excessive temperature and damage the product. Therefore, it is necessary to balance the bias value, reaction temperature and reaction rate.

优选地，在一些实施例中，射频的频率使用20～300KHz，较高的脉冲频率，可以避免绝缘产品表面的电荷持续积累，抑制大电弧现象和增加涂层沉积厚度极限。Preferably, in some embodiments, the frequency of the radio frequency is 20-300KHz, and the higher pulse frequency can avoid the continuous accumulation of charges on the surface of the insulating product, suppress the large arc phenomenon and increase the coating thickness limit.

在所述反应气体原料沉积的阶段，镀膜时间过短形成的膜层较薄，硬度表现差，而镀膜时间过长，厚度增大，但是影响透明性。根据本发明的实施例，当镀膜时间为5-300min时，能够在厚度、硬度以及透明性之间平衡。In the stage of the deposition of the reactive gas raw materials, the film formed by the coating time is too short and the hardness is poor, while the coating time is too long and the thickness increases, but the transparency is affected. According to the embodiment of the present invention, when the coating time is 5-300 minutes, the thickness, hardness and transparency can be balanced.

进一步，在所述增强纳米膜的沉积过程，反应装置内的温度范围为25℃～100℃。优选地，温度范围为25℃～50℃。在上述温度范围对所述基体的影响较小，适于不耐高温的产品，比如适于电子产品。在形成所述增强纳米膜时，可以在产品的单独部件上形成，比如在未组装的电子屏幕上形成，也可以在组装的产品上形成，比如在组装成电子设备的屏幕上形成，工艺条件更加灵活。Further, during the deposition process of the reinforced nano film, the temperature in the reaction device ranges from 25°C to 100°C. Preferably, the temperature range is 25°C to 50°C. In the above-mentioned temperature range, the influence on the substrate is small, and it is suitable for products that are not resistant to high temperatures, such as suitable for electronic products. When forming the reinforced nano film, it can be formed on a separate part of a product, such as on an unassembled electronic screen, or on an assembled product, such as on a screen assembled into an electronic device. The process conditions More flexible.

值得一提的是，主流电子产品屏幕所用材料为高分子材料，其耐热变形能力较差，一般耐温都在100℃一下，作为制造工艺的终端工艺，镀膜处理需要确保改变原材料的性能，所以低温工艺是电子产品加工的硬需求。在制备所述增强纳米膜时，通过与产品摆放等效位置的热电偶来实时检测反应温度，控制反应温度，使其不会影响电子设备。It is worth mentioning that the materials used in mainstream electronic product screens are polymer materials, which have poor resistance to heat deformation. Generally, the temperature resistance is below 100°C. As the final process of the manufacturing process, the coating process needs to ensure that the performance of the raw materials is changed. Therefore, the low temperature process is a hard demand for the processing of electronic products. When preparing the reinforced nano-membrane, the reaction temperature is detected in real time by a thermocouple placed in an equivalent position with the product, and the reaction temperature is controlled so that it will not affect the electronic equipment.

值得一提的是，现有技术中的采用离子交换或者物理气相沉积的方法获取DLC，需要利用高温加热硝酸钾等离子盐形成离子浴，且离子交换时间长，成本较高。而本发明的实施例中，利用PECVD方法直接在电子设备外盖等基体表面沉积掺杂元素的类金刚石薄膜，常温下即可完成，所需时间短，利于成本控制；另一方面，本发明的实施例中通过射频与高压脉冲辅助等离子体化学气相沉积，利用低功率射频放电维持等离子体环境，抑制高压放电过程的弧光放电，与现有技术中的磁控溅射等物理气相沉积法相比整个沉积过程中基体温度低，可应用于 一些不耐高温的电子器件的镀膜。当对电子设备外盖进行强化处理时，可以先将外盖组装完成再进行DLC气相沉积镀膜，也就是说，在电子设备制造完成之后再设置所述增强纳米膜；另一方面，本发明用于外盖增强的DLC纳米涂层制备过程工艺可控性好，通过控制电极放电特性、气体流量、镀膜时间等工艺参数，可方便地获得目标DLC纳米涂层。It is worth mentioning that in the prior art, the method of ion exchange or physical vapor deposition to obtain DLC requires high temperature heating of potassium nitrate plasma salt to form an ion bath, and the ion exchange time is long and the cost is high. In the embodiment of the present invention, the PECVD method is used to directly deposit the element-doped diamond-like carbon film on the surface of the substrate such as the outer cover of the electronic device, which can be completed at room temperature, and the required time is short, which is beneficial to cost control; on the other hand, the present invention In the embodiment, the plasma chemical vapor deposition is assisted by radio frequency and high voltage pulses, and low power radio frequency discharge is used to maintain the plasma environment and suppress the arc discharge in the high voltage discharge process. Compared with the physical vapor deposition methods such as magnetron sputtering in the prior art The substrate temperature is low during the whole deposition process, which can be applied to the coating of some electronic devices that are not resistant to high temperatures. When the outer cover of the electronic device is strengthened, the outer cover can be assembled and then DLC vapor deposition coating is performed, that is, the enhanced nano film is set after the electronic device is manufactured; on the other hand, the present invention uses The preparation process of the DLC nano-coating reinforced on the outer cover has good process controllability, and the target DLC nano-coating can be easily obtained by controlling process parameters such as electrode discharge characteristics, gas flow, and coating time.

参照图2，所述电子设备以智能手机为例，所述电子设备10包括一主体11和一外盖12，所述外盖12被安装于所述主体11的背面。一增强纳米膜20被一体沉积形成于所述外盖12的表面。2, the electronic device is a smart phone as an example. The electronic device 10 includes a main body 11 and an outer cover 12, and the outer cover 12 is installed on the back of the main body 11. A reinforced nano-film 20 is integrally deposited and formed on the surface of the outer cover 12.

进一步，所述外盖12具有一边缘121，所述增强纳米膜20覆盖所述外盖12的边缘121，或者说，所述增强纳米膜20延伸至所述外盖的边缘121。换句话说，所述增强纳米膜20能够完全覆盖所述外盖12的表面，尤其是边缘121位置，减少外盖边缘产生Griffith裂纹。Further, the outer cover 12 has an edge 121, and the reinforced nanomembrane 20 covers the edge 121 of the outer cover 12, or in other words, the reinforced nanomembrane 20 extends to the edge 121 of the outer cover. In other words, the reinforced nanomembrane 20 can completely cover the surface of the outer cover 12, especially the position of the edge 121, thereby reducing Griffith cracks at the edge of the outer cover.

在一个实施例中，所述边缘121呈微弧形，所述增强纳米膜20覆盖微弧形的表面。In one embodiment, the edge 121 has a micro-arc shape, and the reinforced nano-membrane 20 covers the micro-arc surface.

在制备所述增强纳米膜20时，所述电子设备10被水平放置于一PECVD反应装置中30，所述外盖12朝向上方，通入气体40，即所述反应原料气体、所述掺杂气体原料、所述等离子体源气体以及所述辅助气体，在射频电场和高压脉冲电场的共同作用下形成等离子体，并且在电场环境中由上方逐渐沉积于所述外盖12的表面。也就是说，所述增强纳米膜20会随着所述外盖12的形状而成形，或者说依附所述外盖12的表面形状成形，由此可以牢固地连接于所述外盖12表面，并且完全地覆盖所述外盖12的表面。而所述反应气体原料形成的DLC膜的特性以及其与所述显示屏的结合方式整体使得所述增强纳米膜20能够较好地改善所述外盖12的表面性能，比如提高所述外盖12的刚性、耐摔性能以及耐摩擦性能。When preparing the reinforced nano-membrane 20, the electronic device 10 is placed horizontally in a PECVD reaction device 30, the outer cover 12 faces upward, and the gas 40 is introduced, that is, the reaction raw material gas, the doping gas The gas raw materials, the plasma source gas and the auxiliary gas form plasma under the combined action of a radio frequency electric field and a high-voltage pulsed electric field, and are gradually deposited on the surface of the outer cover 12 from above in an electric field environment. That is to say, the reinforced nano-membrane 20 will be shaped according to the shape of the outer cover 12, or shaped according to the surface shape of the outer cover 12, so that it can be firmly connected to the surface of the outer cover 12, And completely cover the surface of the outer cover 12. The characteristics of the DLC film formed by the reactive gas raw materials and its combination with the display screen as a whole enable the enhanced nano film 20 to better improve the surface properties of the outer cover 12, such as improving the outer cover 12 12's rigidity, drop resistance and friction resistance.

值得一提的是，根据Griffith微裂纹理论，由于材料原本带有的微裂纹，应力会容易集中在该位置，而弧形区域或者说结构边缘区域也是应力容易集中的位置，因此在该位置的原始裂纹和结构结合，使得边缘位置容易受损伤，而本发明的实施例中，所述增强纳米膜完全覆盖所述外盖的边缘，并且通过化学沉积的方式一体结合，使得边缘位置的结构稳定性能够得到改善，而降低损伤率。It is worth mentioning that, according to the Griffith microcrack theory, due to the microcracks originally contained in the material, the stress will easily concentrate at this position, and the arc area or the edge area of the structure is also the position where the stress is easy to concentrate. The combination of the original crack and the structure makes the edge position easy to be damaged. In the embodiment of the present invention, the reinforced nano film completely covers the edge of the outer cover, and is integrated by chemical deposition, so that the edge position is stable. Performance can be improved, and the damage rate can be reduced.

值得一提的是，在所述外盖12的表面形成所述增强纳米膜20时，可以在所 述外盖12未组装于所述电子设备主体11时进行，也就是说，其可以由所述显示屏的生产厂商制备形成，也可以在所述外盖12组装于所述主体11时进行，比如所述电子设备10组装完成之后进行，即由电子设备生产商制造完成。所述增强纳米膜的制备可以被灵活地选择在不同的阶段完成，工艺要求降低。It is worth mentioning that when the reinforced nano-membrane 20 is formed on the surface of the outer cover 12, it can be performed when the outer cover 12 is not assembled to the electronic device main body 11, that is, it can be The preparation and formation by the manufacturer of the display screen can also be performed when the outer cover 12 is assembled to the main body 11, for example, after the assembly of the electronic device 10 is completed, that is, the manufacturing is completed by the electronic device manufacturer. The preparation of the reinforced nanomembrane can be flexibly selected to be completed in different stages, and the process requirements are reduced.

以下实施例示例说明通过一PECVD反应装置在一基体表面气相沉积形成所述增强纳米膜的不同过程。The following embodiments illustrate different processes of forming the reinforced nano-film by vapor deposition on a substrate surface by a PECVD reaction device.

实施例1Example 1

一种用于手机玻璃外盖增强的DLC纳米膜制备方法：A method for preparing DLC nano-membrane for strengthening the glass cover of mobile phone:

(1)将手机玻璃后盖用无水乙醇超声清洗10min，再用无尘布将其擦干后置于干燥箱中吹干6h。(1) Ultrasonic clean the glass back cover of the mobile phone with absolute ethanol for 10 minutes, then wipe it dry with a dust-free cloth and place it in a drying oven for 6 hours.

(2)将玻璃屏幕放置于真空反应腔中，进行抽真空使腔体内压力降至0.01Pa以下，通入氩气进行表面刻蚀处理，氩气流量为150sccm，腔体内压力控制在8Pa。打开高压脉冲电源，偏压电源电压为-1000V，占空比为20％，频率为10kHz，处理时间为15min。(2) Place the glass screen in a vacuum reaction chamber, perform vacuuming to reduce the pressure in the chamber to below 0.01 Pa, and pass argon gas for surface etching. The flow rate of argon gas is 150 sccm, and the pressure in the chamber is controlled at 8 Pa. Turn on the high-voltage pulse power supply, the bias power supply voltage is -1000V, the duty cycle is 20%, the frequency is 10kHz, and the processing time is 15min.

(3)关闭氩气，向真空反应腔体中引入甲烷、氢气、六甲基环三硅氧烷，气体流量为150sccm、100sccm、30sccm，压力控制在8Pa，设定偏压电源电压为-1000V，占空比为50％，频率设定为30kHz；打开射频电源输出功率为20W，频率为10kHz。沉积过程时间为15min。(3) Turn off the argon gas, and introduce methane, hydrogen, and hexamethylcyclotrisiloxane into the vacuum reaction chamber. The gas flow is 150sccm, 100sccm, 30sccm, the pressure is controlled at 8Pa, and the bias power supply voltage is set to -1000V , The duty cycle is 50%, and the frequency is set to 30kHz; when the RF power is turned on, the output power is 20W and the frequency is 10kHz. The deposition process time is 15 minutes.

(4)沉积结束后，关闭气源进口阀、电源，充入空气至常压，打开真空反应腔，取出手机玻璃后盖。(4) After the deposition is over, close the gas source inlet valve and power supply, fill with air to normal pressure, open the vacuum reaction chamber, and take out the glass back cover of the mobile phone.

实施例2Example 2

一种用于手机玻璃后盖增强的含有过渡层DLC纳米膜制备方法：A preparation method of a DLC nano film containing a transition layer for the reinforcement of the glass back cover of a mobile phone:

(1)将手机玻璃后盖用无水乙醇超声清洗10min，再用无尘布将其擦干后置于干燥箱中吹干6h。(1) Ultrasonic clean the glass back cover of the mobile phone with absolute ethanol for 10 minutes, then wipe it dry with a dust-free cloth and place it in a drying oven for 6 hours.

(2)将玻璃屏幕放置于真空反应腔中，进行抽真空使腔体内压力降至0.01Pa以下，通入氩气进行表面刻蚀处理，氩气流量为100sccm，腔体内压力控制在10Pa。打开高压脉冲电源，偏压电源电压为-1000V，占空比为50％，频率为40kHz，处理时间为15min。(2) Place the glass screen in a vacuum reaction chamber, evacuate the chamber to reduce the pressure in the chamber to below 0.01 Pa, pass argon gas for surface etching treatment, the argon flow rate is 100 sccm, and the pressure in the chamber is controlled at 10 Pa. Turn on the high-voltage pulse power supply, the bias power supply voltage is -1000V, the duty cycle is 50%, the frequency is 40kHz, and the processing time is 15min.

(3)氩气流量调整为30sccm，向真空反应腔中引入六甲基二硅氧烷制备过 渡层，流量设定为150sccm，开启射频电源，功率为300W，输出频率为100Hz，脉冲宽度设置为3ms，气相沉积时间为30min。(3) Adjust the flow of argon to 30sccm, introduce hexamethyldisiloxane into the vacuum reaction chamber to prepare the transition layer, set the flow to 150sccm, turn on the RF power supply, the power is 300W, the output frequency is 100Hz, and the pulse width is set to 3ms, the vapor deposition time is 30min.

(4)继续向真空反应腔中引入六甲基二硅氧烷，然后向真空反应腔体中引入甲烷、氢气，气体流量为150sccm、100sccm，压力控制在8Pa，设定偏压电源电压为-1000V，占空比为50％，频率设定为30kHz。沉积过程时间为30min。(4) Continue to introduce hexamethyldisiloxane into the vacuum reaction chamber, and then introduce methane and hydrogen into the vacuum reaction chamber, the gas flow is 150sccm, 100sccm, the pressure is controlled at 8Pa, and the bias power supply voltage is set to- 1000V, the duty cycle is 50%, and the frequency is set to 30kHz. The deposition process time is 30 minutes.

(5)沉积结束后，关闭气源进口阀、电源，充入空气至常压，打开真空反应腔，取出手机玻璃后盖。(5) After the deposition is over, close the gas source inlet valve and power supply, fill in air to normal pressure, open the vacuum reaction chamber, and take out the glass back cover of the mobile phone.

实施例3Example 3

与实施例1相比，将步骤(2)中的真空压力将至0.001Pa以下，步骤(3)中的压力控制在20Pa，其他条件不改变。Compared with Example 1, the vacuum pressure in step (2) is reduced to less than 0.001 Pa, the pressure in step (3) is controlled at 20 Pa, and other conditions are not changed.

实施例4Example 4

与实施例1相比，将步骤(3)中的六甲基环三硅氧烷更换为四氟化碳，沉积时间更换为30min，其他条件不改变。Compared with Example 1, the hexamethylcyclotrisiloxane in step (3) was replaced with carbon tetrafluoride, the deposition time was replaced with 30 min, and other conditions were unchanged.

实施例5Example 5

与实施例1相比，将步骤(3)中的六甲基环三硅氧烷更换为八氟丙烯、八氟环丁烷，其流量为50sccm，沉积时间更换为60min，其他条件不改变。Compared with Example 1, the hexamethylcyclotrisiloxane in step (3) was replaced with octafluoropropene and octafluorocyclobutane, the flow rate was 50 sccm, and the deposition time was replaced with 60 min, and other conditions were unchanged.

实施例6Example 6

与实施例5相比，将步骤(3)中的六甲基环三硅氧烷更换为己硼烷，流量为50sccm，将氢气流量设置为0，其他条件不改变。Compared with Example 5, the hexamethylcyclotrisiloxane in step (3) was replaced with hexaborane, the flow rate was 50 sccm, the hydrogen flow rate was set to 0, and other conditions were not changed.

实施例7Example 7

与实施例5相比，将步骤(3)中的甲烷更换为乙炔，六甲基环三硅氧烷更换为氮气，其他条件不改变。Compared with Example 5, the methane in step (3) was replaced with acetylene, and the hexamethylcyclotrisiloxane was replaced with nitrogen, and the other conditions were unchanged.

实施例8Example 8

与实施例5相比，在步骤(3)中增加通入八氟丙烯、八氟环丁烷，流量为 30sccm，其他条件不改变。Compared with Example 5, octafluoropropylene and octafluorocyclobutane were added in step (3), and the flow rate was 30 sccm, and other conditions remained unchanged.

实施例9Example 9

与实施例7相比，不通入六甲基环三硅氧烷，其他条件不变。Compared with Example 7, hexamethylcyclotrisiloxane was not passed through, and other conditions remained unchanged.

以下对上述实施例整体进行检测。The entire above-mentioned embodiment is tested as follows.

厚度测试方法，使用美国Filmetrics F20-UV-薄膜厚度测量仪进行检测。Thickness test method, use American Filmetrics F20-UV-film thickness measuring instrument for testing.

在计算薄膜残余应力前，先用接触式轮廓仪PGI Optics测量了基底镀膜前和镀膜后的面形。将轮廓仪测得的数据利用最小二乘法进行拟合，得到曲率半径，最后通过Stoney公式进行计算，得到DLC薄膜残余应力的大小。Before calculating the residual stress of the film, the contact profiler PGI Optics was used to measure the surface shape of the substrate before and after coating. The data measured by the profiler is fitted by the least square method to obtain the radius of curvature, and finally calculated by the Stoney formula to obtain the residual stress of the DLC film.

耐磨性测试，在酒精耐磨试验机进行，选择橡皮擦测试夹具进行测试，测试条件为载荷1000g，转速为60cycle/min，测试膜破坏时的循环次数。The abrasion resistance test was carried out in an alcohol abrasion tester, and the eraser test fixture was selected for the test. The test conditions were a load of 1000 g, a rotation speed of 60 cycle/min, and the number of cycles when the film was broken.

耐摔性测试，将手机从距水泥地1m高处自由下落，重复试验至屏幕产生明显裂纹。In the drop resistance test, the mobile phone was dropped freely from a height of 1m from the concrete floor, and the test was repeated until the screen had obvious cracks.

实施例Example	厚度/nmThickness/nm	耐摩擦次数Resistance to friction	应力(GPa)Stress (GPa)	耐摔次数Resistance to fall
实施例1Example 1	22twenty two	5600056000	1.11.1	1515
实施例2Example 2	4242	6500065,000	1.51.5	1919
实施例3Example 3	2727	5100051000	1.81.8	1414
实施例4Example 4	4747	5300053000	3.83.8	1818
实施例5Example 5	4949	5500055,000	3.73.7	1111
实施例6Example 6	3838	4800048000	2.12.1	1414
实施例7Example 7	106106	5100051000	1.91.9	1313
实施例8Example 8	5454	5600056000	3.13.1	1313
实施例9Example 9	9898	4200042000	7.97.9	1212
未镀膜玻璃后盖Uncoated glass back cover	00	--	--	55

由上述实施例测试结果可以看出，掺杂元素的DLC薄膜形成于手机外盖后，手机外盖的残余应力相对较小，耐摔性能普遍提高。It can be seen from the test results of the foregoing embodiments that after the element-doped DLC film is formed on the outer cover of the mobile phone, the residual stress of the outer cover of the mobile phone is relatively small, and the drop resistance is generally improved.

本领域的技术人员应理解，上述描述及附图中所示的本发明的实施例只作为 举例而并不限制本发明。本发明的优势已经完整并有效地实现。本发明的功能及结构原理已在实施例中展示和说明，在没有背离所述原理下，本发明的实施方式可以有任何变形或修改。Those skilled in the art should understand that the embodiments of the present invention shown in the above description and the accompanying drawings are only examples and do not limit the present invention. The advantages of the present invention have been completely and effectively realized. The functions and structural principles of the present invention have been shown and explained in the embodiments. Without departing from the principles, the implementation of the present invention may have any deformation or modification.

Claims (81)

1. 一增强纳米膜，其特征在于，包括：C、H和一掺杂元素，其以碳氢气体C _xH _y和至少一掺杂气体作为反应气体原料，通过PECVD工艺在一基体的表面沉积形成，其中所述掺杂气体提供所述掺杂元素。 A reinforced nano film, characterized by comprising: C, H and a doping element, which uses hydrocarbon gas C _x H _y and at least one doping gas as raw materials for reaction gas, and is formed by depositing on the surface of a substrate through a PECVD process , Wherein the doping gas provides the doping element.
2. 根据权利要求1所述的增强纳米膜，其中碳氢气体C _xH _y是碳原子数为1-6的烷烃、烯烃、炔烃或者苯中的其中一种或多种。 The reinforced nanomembrane according to claim 1, wherein the hydrocarbon gas C _x H _y is one or more of alkane, alkene, alkyne or benzene with carbon number of 1-6.
3. 根据权利要求1所述的增强纳米膜，其中所述掺杂元素选自Si、N、F、B中的一种或多种。The reinforced nanomembrane according to claim 1, wherein the doping element is selected from one or more of Si, N, F, and B.
4. 根据权利要求3所述的增强纳米膜，其中掺杂Si元素的所述掺杂气体原料是含硅有机化合物，包括有机直链硅氧烷、环硅氧烷、烷氧基硅烷、含不饱和碳碳双键硅氧烷。The reinforced nanomembrane according to claim 3, wherein the raw material of the doping gas doped with Si element is a silicon-containing organic compound, including organic linear siloxane, cyclosiloxane, alkoxysilane, and unsaturated Carbon-carbon double bond siloxane.
5. 根据权利要求3所述的增强纳米膜，其中掺杂N元素的所述掺杂气体原料是N ₂、含氮碳氢化合物。 3. The reinforced nano film according to claim 3, wherein the doping gas raw material doped with N element is N ₂ , a nitrogen-containing hydrocarbon.
6. 根据权利要求3所述的增强纳米膜，其中掺杂F元素的所述掺杂气体原料是氟碳气体。3. The reinforced nano film according to claim 3, wherein the doping gas raw material doped with the F element is a fluorocarbon gas.
7. 根据权利要求6所述的增强纳米膜，其中氟碳气体选自四氟化碳、八氟丙烯、八氟环丁烷中的一种或多种。The reinforced nanomembrane according to claim 6, wherein the fluorocarbon gas is selected from one or more of carbon tetrafluoride, octafluoropropylene, and octafluorocyclobutane.
8. 根据权利要求3所述的增强纳米膜，其中掺杂B元素的所述掺杂气体原料是常压下沸点低于300℃的硼烷。The reinforced nanomembrane according to claim 3, wherein the dopant gas raw material doped with element B is borane with a boiling point lower than 300° C. under normal pressure.
9. 根据权利要求8所述的增强纳米膜，其中硼烷选自戊硼烷、己硼烷中的一种或多种。8. The reinforced nanomembrane according to claim 8, wherein the borane is selected from one or more of pentaborane and hexaborane.
10. 根据权利要求1-9任一所述的增强纳米膜，其中在进行PECVD工艺时，加入一等离子体源气体，以激活所述反应气体原料的沉积反应。9. The reinforced nano film according to any one of claims 1-9, wherein a plasma source gas is added during the PECVD process to activate the deposition reaction of the reactive gas raw materials.
11. 根据权利要求10所述的增强纳米膜，其中所述等离子体源气体选自惰性气体、氮气、氟碳气体中的其中一种或多种。10. The reinforced nanomembrane according to claim 10, wherein the plasma source gas is selected from one or more of inert gas, nitrogen, and fluorocarbon gas.
12. 根据权利要求1-9任一所述的增强纳米膜，其中在进行PECVD工艺时，加入一辅助气体，与所述反应气体原料共同沉积反应，其中所述辅助气体是氢气，以调节所述增强纳米膜中的C-H键含量。8. The reinforced nanomembrane according to any one of claims 1-9, wherein during the PECVD process, an auxiliary gas is added to co-deposit and react with the reaction gas raw material, wherein the auxiliary gas is hydrogen to adjust the enhancement The content of CH bonds in the nanomembrane.
13. 根据权利要求12所述的增强纳米膜，其中所述氢气的含量≤40％。The reinforced nanomembrane according to claim 12, wherein the content of hydrogen is ≤40%.
14. 根据权利要求1-9任一所述的增强纳米膜，其中在进行PECVD工艺时，射频和高压脉冲共同作用沉积形成所述增强纳米膜。8. The reinforced nanomembrane according to any one of claims 1-9, wherein when the PECVD process is performed, radio frequency and high-voltage pulses work together to form the reinforced nanomembrane.
15. 根据权利要求14所述的增强纳米膜，其中所述射频功率范围为10～800W，脉冲电源电压-100V～-5000V，脉冲占空比10％～80％。The reinforced nanomembrane according to claim 14, wherein the radio frequency power range is 10-800W, the pulse power supply voltage is -100V-5000V, and the pulse duty ratio is 10%-80%.
16. 根据权利要求1-9任一所述的增强纳米膜，其中所述基体是一电子设备外盖。The reinforced nanomembrane according to any one of claims 1-9, wherein the substrate is an electronic device outer cover.
17. 根据权利要求16所述的增强纳米膜，其中所述电子设备选自于智能手机、平板电脑、电子阅读器、可穿戴设备、电视机、电脑显示屏中的一种。The reinforced nanomembrane according to claim 16, wherein the electronic device is selected from one of a smart phone, a tablet computer, an e-reader, a wearable device, a television, and a computer display screen.
18. 一增强纳米膜的制备方法，其特征在于，以碳氢气体C _xH _y和至少一掺杂气体作为反应气体原料，通过PECVD装置在一基体的表面沉积形成，其中所述掺杂气体提供至少一掺杂元素。 A method for preparing an enhanced nano-film is characterized in that hydrocarbon gas C _x H _y and at least one doping gas are used as raw materials for reacting gas, which are deposited on the surface of a substrate by a PECVD device, wherein the doping gas provides at least One doping element.
19. 根据权利要求18所述的增强纳米膜的制备方法，其中包括步骤：向所述PECVD装置通入一等离子体源气体，以激活所述反应气体原料的沉积反应。18. The method for preparing a reinforced nano-film according to claim 18, which comprises the step of passing a plasma source gas into the PECVD device to activate the deposition reaction of the reactive gas material.
20. 根据权利要求19所述的增强纳米膜的制备方法，其中所述等离子体源气体选自惰性气体、氮气、氟碳气体中的其中一种或多种。The method for preparing a reinforced nanomembrane according to claim 19, wherein the plasma source gas is selected from one or more of inert gas, nitrogen, and fluorocarbon gas.
21. 根据权利要求19所述的增强纳米膜的制备方法，其中包括步骤：打开所述PECVD装置的一高压脉冲电源，所述等离子体源气体在高压脉冲电场的作用下清洁所述基体表面，并且蚀刻和活化。The method for preparing a reinforced nano-membrane according to claim 19, which comprises the steps of: turning on a high-voltage pulse power supply of the PECVD device, the plasma source gas cleans the surface of the substrate under the action of the high-voltage pulse electric field, and etching And activation.
22. 根据权利要求21所述的增强纳米膜的制备方法，其中高压脉冲电源电压-100V～-5000V、占空比1％～90％。22. The method for preparing a reinforced nanomembrane according to claim 21, wherein the high-voltage pulse power supply voltage is -100V-5000V, and the duty ratio is 1%-90%.
23. 根据权利要求18所述的增强纳米膜的制备方法，其中在进行PECVD工艺时，加入一辅助气体，与所述反应气体原料共同沉积反应，其中所述辅助气体是氢气，以调节所述增强纳米膜中的C-H键含量。The method for preparing an enhanced nano-film according to claim 18, wherein during the PECVD process, an auxiliary gas is added to co-deposit and react with the reaction gas raw material, wherein the auxiliary gas is hydrogen to adjust the enhanced nano-film The content of CH bonds in the film.
24. 根据权利要求23所述的增强纳米膜的制备方法，其中所述氢气的含量≤40％。The method for preparing a reinforced nanomembrane according to claim 23, wherein the content of the hydrogen is ≤40%.
25. 根据权利要求18-24任一所述的增强纳米膜的制备方法，其中在进行PECVD工艺时，射频和高压脉冲共同作用沉积形成所述增强纳米膜。24. The method for preparing an enhanced nano-film according to any one of claims 18-24, wherein when the PECVD process is performed, radio frequency and high-voltage pulses work together to deposit the enhanced nano-film.
26. 根据权利要求25所述的增强纳米膜的制备方法，其中所述射频功率范围为10～800W，脉冲电源电压-100V～-5000V，脉冲占空比10％～80％。The method for preparing the reinforced nanomembrane according to claim 25, wherein the radio frequency power range is 10-800W, the pulse power supply voltage is -100V-5000V, and the pulse duty ratio is 10%-80%.
27. 根据权利要求18-24任一所述的增强纳米膜的制备方法，其中所述基体 是一电子设备外盖。The method for preparing a reinforced nanomembrane according to any one of claims 18-24, wherein the substrate is an electronic device outer cover.
28. 根据权利要求27所述的增强纳米膜的制备方法，其中所述电子设备选自于智能手机、平板电脑、电子阅读器、可穿戴设备、电视机、电脑显示屏中的一种。27. The method for preparing a reinforced nanomembrane according to claim 27, wherein the electronic device is selected from one of a smart phone, a tablet computer, an e-reader, a wearable device, a television, and a computer display screen.
29. 根据权利要求18-24任一所述的增强纳米膜的制备方法，其中碳氢气体C _xH _y是碳原子数为1-6的烷烃、烯烃、炔烃或者苯中的其中一种或多种。 The method for preparing a reinforced nanomembrane according to any one of claims 18-24, wherein the hydrocarbon gas C _x H _y is one or more of alkane, alkene, alkyne or benzene with carbon number of 1-6. Kind.
30. 根据权利要求18-24任一所述的增强纳米膜的制备方法，其中所述掺杂元素选自Si、N、F、B中的一种或多种。The method for preparing a reinforced nanomembrane according to any one of claims 18-24, wherein the doping element is selected from one or more of Si, N, F, and B.
31. 根据权利要求30所述的增强纳米膜的制备方法，其中掺杂Si元素的所述掺杂气体原料是含硅有机化合物，包括有机直链硅氧烷、环硅氧烷、烷氧基硅烷、含不饱和碳碳双键硅氧烷。The method for preparing a reinforced nanomembrane according to claim 30, wherein the doping gas raw material doped with Si element is a silicon-containing organic compound, including organic linear siloxane, cyclosiloxane, alkoxysilane, Containing unsaturated carbon-carbon double bond siloxane.
32. 根据权利要求30所述的增强纳米膜的制备方法，其中掺杂N元素的所述掺杂气体原料是N ₂、含氮碳氢化合物。 The method for preparing a reinforced nanomembrane according to claim 30, wherein the doping gas raw material doped with N element is N ₂ and nitrogen-containing hydrocarbons.
33. 根据权利要求30所述的增强纳米膜的制备方法，其中掺杂F元素的所述掺杂气体原料是氟碳气体。The method for preparing a reinforced nanomembrane according to claim 30, wherein the doping gas raw material doped with the F element is a fluorocarbon gas.
34. 根据权利要求33所述的增强纳米膜的制备方法，其中氟碳气体选自四氟化碳、八氟丙烯、八氟环丁烷中的一种或多种。The method for preparing a reinforced nanomembrane according to claim 33, wherein the fluorocarbon gas is selected from one or more of carbon tetrafluoride, octafluoropropylene, and octafluorocyclobutane.
35. 根据权利要求30所述的增强纳米膜的制备方法，其中掺杂B元素的所述掺杂气体原料是常压下沸点低于300℃的硼烷。The method for preparing a reinforced nanomembrane according to claim 30, wherein the doping gas raw material doped with element B is borane with a boiling point lower than 300° C. under normal pressure.
36. 根据权利要求35所述的增强纳米膜的制备方法，其中硼烷选自戊硼烷、己硼烷中的一种或多种。The method for preparing a reinforced nanomembrane according to claim 35, wherein the borane is selected from one or more of pentaborane and hexaborane.
37. 一电子设备，其特征在于，包括：An electronic device, characterized in that it includes:

    一主体；A subject

    一外盖；和An outer cover; and

    一增强纳米膜，其中所述增强纳米膜包括C、H和一掺杂元素，其以碳氢气体C _xH _y和至少一掺杂气体作为反应气体原料，通过PECVD工艺在一基体的表面沉积形成，其中所述掺杂气体提供所述掺杂元素，其中所述外盖被安装于所述主体背面，所述增强纳米膜通过PECVD工艺沉积于所述外盖的表面。 An enhanced nano film, wherein the enhanced nano film includes C, H and a doping element, which uses hydrocarbon gas C _x H _y and at least one dopant gas as raw materials for reaction gas, and is deposited on the surface of a substrate through a PECVD process Forming, wherein the doping gas provides the doping element, wherein the outer cover is installed on the back of the main body, and the reinforced nano film is deposited on the surface of the outer cover through a PECVD process.
38. 根据权利要求37所述的电子设备，其中碳氢气体C _xH _y是碳原子数为1-6的烷烃、烯烃、炔烃或者苯中的其中一种或多种。 The electronic device according to claim 37, wherein the hydrocarbon gas C _x H _y is one or more of alkane, alkene, alkyne or benzene with carbon number of 1-6.
39. 根据权利要求37所述的电子设备，其中所述掺杂元素选自Si、N、F、B中的一种或多种。The electronic device according to claim 37, wherein the doping element is selected from one or more of Si, N, F, and B.
40. 根据权利要求39所述的电子设备，其中掺杂Si元素的所述掺杂气体原料是含硅有机化合物，包括有机直链硅氧烷、环硅氧烷、烷氧基硅烷、含不饱和碳碳双键硅氧烷。The electronic device according to claim 39, wherein said dopant gas raw material doped with Si element is a silicon-containing organic compound, including organic linear siloxane, cyclosiloxane, alkoxysilane, and unsaturated carbon-containing Carbon double bond siloxane.
41. 根据权利要求39所述的电子设备，其中掺杂N元素的所述掺杂气体原料是N ₂、含氮碳氢化合物。 The electronic device according to claim 39, wherein said dopant gas raw material doped with N element is N ₂ , a nitrogen-containing hydrocarbon.
42. 根据权利要求39所述的电子设备，其中掺杂F元素的所述掺杂气体原料是氟碳气体。The electronic device according to claim 39, wherein said doping gas raw material doped with F element is a fluorocarbon gas.
43. 根据权利要求42所述的电子设备，其中氟碳气体选自四氟化碳、八氟丙烯、八氟环丁烷中的一种或多种。The electronic device according to claim 42, wherein the fluorocarbon gas is selected from one or more of carbon tetrafluoride, octafluoropropylene, and octafluorocyclobutane.
44. 根据权利要求39所述的电子设备，其中掺杂B元素的所述掺杂气体原料是常压下沸点低于300℃的硼烷。The electronic device according to claim 39, wherein said dopant gas raw material doped with element B is borane having a boiling point of less than 300°C under normal pressure.
45. 根据权利要求44所述的电子设备，其中硼烷选自戊硼烷、己硼烷中的一种或多种。The electronic device according to claim 44, wherein the borane is selected from one or more of pentaborane and hexaborane.
46. 根据权利要求37-45任一所述的电子设备，其中在进行PECVD工艺时，加入一等离子体源气体，以激活所述反应气体原料的沉积反应。The electronic device according to any one of claims 37-45, wherein a plasma source gas is added during the PECVD process to activate the deposition reaction of the reactive gas raw materials.
47. 根据权利要求46所述的电子设备，其中所述等离子体源气体选自惰性气体、氮气、氟碳气体中的其中一种或多种。The electronic device according to claim 46, wherein the plasma source gas is selected from one or more of inert gas, nitrogen, and fluorocarbon gas.
48. 根据权利要求37-45任一所述的电子设备，其中在进行PECVD工艺时，加入一辅助气体，与所述反应气体原料共同沉积反应，其中所述辅助气体是氢气，以调节所述增强纳米膜中的C-H键含量。The electronic device according to any one of claims 37-45, wherein when the PECVD process is performed, an auxiliary gas is added to co-deposit and react with the reaction gas raw material, wherein the auxiliary gas is hydrogen to adjust the enhanced nano The content of CH bonds in the film.
49. 根据权利要求48所述的电子设备，其中所述氢气的含量≤40％。The electronic device according to claim 48, wherein the content of the hydrogen is ≤40%.
50. 根据权利要求37-45任一所述的电子设备，其中在进行PECVD工艺时，射频和高压脉冲共同作用沉积形成所述增强纳米膜。The electronic device according to any one of claims 37-45, wherein when the PECVD process is performed, radio frequency and high-voltage pulses work together to deposit the enhanced nano-film.
51. 根据权利要求50所述的电子设备，其中所述射频功率范围为10～800W，脉冲电源电压-100V～-5000V，脉冲占空比10％～80％。The electronic device according to claim 50, wherein the radio frequency power range is 10-800W, the pulse power supply voltage is -100V-5000V, and the pulse duty ratio is 10%-80%.
52. 根据权利要求37-45任一所述的电子设备，其中所述基体是一电子设备外盖。The electronic device according to any one of claims 37-45, wherein the substrate is an electronic device outer cover.
53. 根据权利要求52所述的电子设备，其中所述电子设备选自于智能手机、 平板电脑、电子阅读器、可穿戴设备、电视机、电脑显示屏中的一种。The electronic device according to claim 52, wherein the electronic device is selected from one of a smart phone, a tablet computer, an e-reader, a wearable device, a television, and a computer display screen.
54. 根据权利要求37至45任一所述的电子设备，其中所述外盖具有一边缘，所述增强纳米膜进一步覆盖所述外盖的边缘。The electronic device according to any one of claims 37 to 45, wherein the outer cover has an edge, and the reinforced nano film further covers the edge of the outer cover.
55. 一电子设备，其特征在于，包括：An electronic device, characterized in that it includes:

    一主体；A subject

    一外盖；和An outer cover; and

    一增强纳米膜，所述外盖被安装于所述主体背面，所述增强纳米膜通过PECVD工艺沉积于所述外盖的表面，其中所述增强纳米膜的制备方法包括以下步骤：A reinforced nanomembrane, the outer cover is installed on the back of the main body, the reinforced nanomembrane is deposited on the surface of the outer cover by a PECVD process, and the preparation method of the reinforced nanomembrane includes the following steps:

    以碳氢气体C _xH _y和至少一掺杂气体作为反应气体原料，通过PECVD装置在一基体的表面沉积形成，其中所述掺杂气体提供至少一掺杂元素。 The hydrocarbon gas C _x H _y and at least one doping gas are used as raw materials for the reaction gas, which are deposited on the surface of a substrate by a PECVD device, wherein the doping gas provides at least one doping element.
56. 根据权利要求55所述的电子设备，其中包括步骤：向所述PECVD装置通入一等离子体源气体，以激活所述反应气体原料的沉积反应。The electronic device according to claim 55, further comprising the step of passing a plasma source gas into the PECVD device to activate the deposition reaction of the reactive gas material.
57. 根据权利要求56所述的电子设备，其中所述等离子体源气体选自惰性气体、氮气、氟碳气体中的其中一种或多种。The electronic device according to claim 56, wherein the plasma source gas is selected from one or more of inert gas, nitrogen, and fluorocarbon gas.
58. 根据权利要求56所述的电子设备，其中包括步骤：打开所述PECVD装置的一高压脉冲电源，所述等离子体源气体在高压脉冲电场的作用下清洁所述基体表面，并且蚀刻和活化。The electronic device according to claim 56, which comprises the step of turning on a high-voltage pulse power supply of the PECVD device, and the plasma source gas cleans the surface of the substrate under the action of the high-voltage pulse electric field, and etches and activates it.
59. 根据权利要求57所述的电子设备，其中高压脉冲电源电压-100V～-5000V、占空比1％～90％。The electronic device according to claim 57, wherein the high-voltage pulse power supply has a voltage of -100V to -5000V and a duty ratio of 1% to 90%.
60. 根据权利要求55所述的电子设备，其中在进行PECVD工艺时，加入一辅助气体，与所述反应气体原料共同沉积反应，其中所述辅助气体是氢气，以调节所述增强纳米膜中的C-H键含量。55. The electronic device according to claim 55, wherein during the PECVD process, an auxiliary gas is added to co-deposit and react with the reactive gas raw material, wherein the auxiliary gas is hydrogen to adjust the CH in the reinforced nano film Bond content.
61. 根据权利要求60所述的电子设备，其中所述氢气的含量≤40％。The electronic device according to claim 60, wherein the content of the hydrogen is ≤40%.
62. 根据权利要求55-61任一所述的电子设备，其中在进行PECVD工艺时，射频和高压脉冲共同作用沉积形成所述增强纳米膜。The electronic device according to any one of claims 55-61, wherein when the PECVD process is performed, radio frequency and high-voltage pulses work together to deposit the enhanced nano-film.
63. 根据权利要求62所述的所述的电子设备，其中所述射频功率范围为10～800W，脉冲电源电压-100V～-5000V，脉冲占空比10％～80％。The electronic device according to claim 62, wherein the radio frequency power range is 10-800W, the pulse power supply voltage is -100V-5000V, and the pulse duty ratio is 10%-80%.
64. 根据权利要求55-61任一所述的所述的电子设备，其中所述基体是一电子设备外盖。The electronic device according to any one of claims 55-61, wherein the base is an electronic device outer cover.
65. 根据权利要求64所述的电子设备，其中所述电子设备选自于智能手机、平 板电脑、电子阅读器、可穿戴设备、电视机、电脑显示屏中的一种。The electronic device according to claim 64, wherein the electronic device is selected from one of a smart phone, a tablet computer, an e-reader, a wearable device, a television, and a computer display screen.
66. 根据权利要求55-61任一所述的电子设备，其中碳氢气体C _xH _y是碳原子数为1-6的烷烃、烯烃、炔烃或者苯中的其中一种或多种。 The electronic device according to any one of claims 55-61, wherein the hydrocarbon gas C _x H _y is one or more of alkane, alkene, alkyne or benzene with carbon number of 1-6.
67. 根据权利要求55-61任一所述的电子设备，其中所述掺杂元素选自Si、N、F、B中的一种或多种。The electronic device according to any one of claims 55-61, wherein the doping element is selected from one or more of Si, N, F, and B.
68. 根据权利要求67所述的电子设备，其中掺杂Si元素的所述掺杂气体原料可以是含硅有机化合物，包括有机直链硅氧烷、环硅氧烷、烷氧基硅烷、含不饱和碳碳双键硅氧烷。The electronic device according to claim 67, wherein said dopant gas raw material doped with Si element may be a silicon-containing organic compound, including organic linear siloxane, cyclosiloxane, alkoxysilane, and unsaturated Carbon-carbon double bond siloxane.
69. 根据权利要求67所述的电子设备，其中掺杂N元素的所述掺杂气体原料是N ₂、含氮碳氢化合物。 The electronic device according to claim 67, wherein said dopant gas raw material doped with N element is N ₂ , a nitrogen-containing hydrocarbon.
70. 根据权利要求67所述的电子设备，其中掺杂F元素的所述掺杂气体原料是氟碳气体。The electronic device according to claim 67, wherein said dopant gas raw material doped with F element is fluorocarbon gas.
71. 根据权利要求70所述的电子设备，其中氟碳气体选自四氟化碳、八氟丙烯、八氟环丁烷中的一种或多种。The electronic device according to claim 70, wherein the fluorocarbon gas is selected from one or more of carbon tetrafluoride, octafluoropropylene, and octafluorocyclobutane.
72. 根据权利要求67所述的电子设备，其中掺杂B元素的所述掺杂气体原料是常压下沸点低于300℃的硼烷。The electronic device according to claim 67, wherein said dopant gas raw material doped with element B is borane having a boiling point of less than 300°C under normal pressure.
73. 根据权利要求72所述的电子设备，其中硼烷选自戊硼烷、己硼烷中的一种或多种。The electronic device according to claim 72, wherein the borane is selected from one or more of pentaborane and hexaborane.
74. 根据权利要求63至61任一所述的电子设备，其中所述外盖具有一边缘，所述增强纳米膜进一步覆盖所述显示屏的边缘。The electronic device according to any one of claims 63 to 61, wherein the outer cover has an edge, and the reinforced nano film further covers the edge of the display screen.
75. 一电子设备外盖表面增强的方法，其特征在于，将一电子设备暴露于一包含结构式C _xH _y的反应原料气体和一掺杂气体反应原料气体中进行等离子体增强化学气相沉积以使得增强纳米膜在所述电子设备外盖的表面形成。 A method for enhancing the surface of the outer cover of an electronic device, which is characterized in that an electronic device is exposed to a _{reaction source gas containing a structural formula C x} H _y and a doping gas reaction source gas for plasma enhanced chemical vapor deposition to make the enhancement The nano film is formed on the surface of the outer cover of the electronic device.
76. 根据权利要求75所述的电子设备外盖表面增强的方法，其中包括步骤：将洁净的所述电子设备放置于一PECVD装置的真空反应腔中，进行抽真空使腔体内压力降至0.01Pa以下；和The method for enhancing the surface of an outer cover of an electronic device according to claim 75, which comprises the step of: placing the clean electronic device in a vacuum reaction chamber of a PECVD device, and performing vacuuming to reduce the pressure in the chamber to less than 0.01 Pa ;with

    通入等离子体源气体进行表面刻蚀处理，腔体内压力控制在10Pa；The plasma source gas is introduced for surface etching treatment, and the pressure in the cavity is controlled at 10 Pa;

    打开高压脉冲电源和射频电源的至少其中一个；Turn on at least one of the high-voltage pulse power supply and the radio frequency power supply;

    其中向所述真空反应腔体中引入甲烷、氢气、六甲基环三硅氧烷，以制得含氢类增强纳米膜。Wherein, methane, hydrogen, and hexamethylcyclotrisiloxane are introduced into the vacuum reaction chamber to prepare hydrogen-containing reinforced nano-membrane.
77. 根据权利要求76所述的电子设备外盖表面增强的方法，其中向所述真空反应腔体中引入甲烷、氢气、六甲基环三硅氧烷，气体流量分别为150sccm、100sccm、30sccm，压力控制在8Pa。The method for enhancing the surface of the outer cover of an electronic device according to claim 76, wherein methane, hydrogen, and hexamethylcyclotrisiloxane are introduced into the vacuum reaction chamber, and the gas flow rate is 150 sccm, 100 sccm, and 30 sccm, respectively. Control at 8Pa.
78. 根据权利要求76所述的电子设备外盖表面增强的方法，其中高压脉冲电源电压-100V～-5000V、占空比1％～90％。The method for enhancing the surface of the outer cover of an electronic device according to claim 76, wherein the high-voltage pulse power supply has a voltage of -100V to -5000V and a duty ratio of 1% to 90%.
79. 根据权利要求76所述的电子设备外盖表面增强的方法，其中高压脉冲电源电压为-1000V、占空比50％。The method for enhancing the surface of the outer cover of an electronic device according to claim 76, wherein the high-voltage pulse power supply voltage is -1000V and the duty ratio is 50%.
80. 根据权利要求76所述的电子设备外盖表面增强的方法，其中所述氢气的含量≤40％。The method for enhancing the surface of the outer cover of an electronic device according to claim 76, wherein the content of the hydrogen is ≤40%.
81. 根据权利要求75所述的电子设备外盖表面增强的方法，其中包括步骤：将所述电子设备水平放置沉积形成所述增强纳米膜。The method for enhancing the surface of the outer cover of an electronic device according to claim 75, wherein the method comprises the step of depositing the electronic device horizontally to form the enhanced nano-film.

Images