CN101475173A - Method for preparing super-hydrophobic antireflex micron and nano composite structure surface - Google Patents
Method for preparing super-hydrophobic antireflex micron and nano composite structure surface Download PDFInfo
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Abstract
本发明属于复合结构表面的制备技术领域,具体涉及一种微米和纳米复合结构的超疏水抗反射硅表面的制备方法。包括硅片的清洁处理,在硅片的表面制作微米级硅岛及网格结构,以银或金纳米粒子为阻挡进行催化刻蚀,得到微米和纳米复合结构表面,及对复合结构表面进行化学修饰等步骤。利用本发明所述方法所制备的超疏水抗反射材料表面与水的静态接触角大于150°,水的静态滚动角小于3°。此表面抗反射性能优越,尤其在800nm到1100nm波长范围内的光反射率小于3%。应用本发明方法,可规模化生产微纳复合结构的超疏水抗反射硅表面,并可以广泛的应用于太阳能电池、微流体芯片、光电器件等方面,具有良好的工业应用前景。
The invention belongs to the technical field of preparation of composite structure surfaces, and in particular relates to a method for preparing superhydrophobic anti-reflection silicon surfaces of micron and nanometer composite structures. Including cleaning of silicon wafers, making micron-scale silicon islands and grid structures on the surface of silicon wafers, catalytic etching with silver or gold nanoparticles as barriers, obtaining micro- and nano-composite structure surfaces, and chemically performing composite structure surfaces modification steps. The static contact angle between the surface of the superhydrophobic anti-reflection material prepared by the method of the invention and water is greater than 150°, and the static rolling angle of water is less than 3°. The surface has excellent anti-reflection performance, especially the light reflectance in the wavelength range of 800nm to 1100nm is less than 3%. By applying the method of the invention, the superhydrophobic anti-reflection silicon surface of the micro-nano composite structure can be produced on a large scale, and can be widely used in solar cells, microfluidic chips, photoelectric devices, etc., and has good industrial application prospects.
Description
技术领域 technical field
本发明属于复合结构表面的制备技术领域,具体涉及一种微米和纳米复合结构的超疏水抗反射硅表面的制备方法。The invention belongs to the technical field of preparation of composite structure surfaces, and in particular relates to a method for preparing superhydrophobic anti-reflection silicon surfaces of micron and nanometer composite structures.
背景技术 Background technique
近年来世界各国对微电系统(MEMS)给予了极大的热情和关注,它正成为新崛起的大规模的产业,成为国民经济新的增长点,并对国防科技的发展产生重大影响。但随着器件和系统的微型化,其特征尺度减小,表面积(L2)和体积(L3)之比值也相对增大,表面效应增强,在宏观尺度中被忽略了的表面力现在起主导作用,由此产生表面摩擦、磨损、粘附和压力损失等一系列问题,使得(MEMS)器件受到了极大的困扰。In recent years, countries all over the world have given great enthusiasm and attention to MEMS. It is becoming a new large-scale industry, a new growth point of the national economy, and has a significant impact on the development of national defense technology. However, with the miniaturization of devices and systems, the characteristic scale decreases, the ratio of surface area (L 2 ) to volume (L 3 ) increases relatively, and the surface effect increases. The leading role, resulting in a series of problems such as surface friction, wear, adhesion and pressure loss, which makes (MEMS) devices suffer greatly.
超疏水表面一般是指与水的接触角大于150°的表面。它具有特殊浸润性质,具有防水、防雾、抗清洁、抗氧化等重要特点,在科学研究和生产、生活等诸多领域有广泛的应用前景,例如可应用在镜片、光学器件、纺织品、机械产品、管道运输、微流体芯片等。这一类特殊性质能够减小器件表面的粘附力和摩擦力,改善液体在微流体器件内的流动性能。日本筑波大学机械工程实验室YasuhisaAndo发表在Sensors and Actuators,Vol.57No.2(1996),p,83~89的论文及法国的V.Studer发表在AppI.Phys.Lett.80,3614(2002)的论文中对超疏水表面的应用进行了尝试性研究。对固体材料表面进行超疏水修饰的方法主要有两种:一种是在接触角大于90°的疏水表面构筑粗糙的微纳米结构;另一种是在表面修饰低表面能的物质,如江雷发表在Adv.Mater.2002,14:1857~180中所说明。结合上述两种方法的固体表面疏水修饰也已经有一些报道。例如(中国专利,公开号CN1378581A,CN1613565A,CN1624062A),Langmuir2008,24,10421~10426。但是上述的一些构筑超疏水表面的方法一般工艺比较复杂,而且需要特殊的仪器和设备,难于实现大面积的制备。因此,探索新的廉价的超疏水制备技术有更重要的价值。A superhydrophobic surface generally refers to a surface with a contact angle with water greater than 150°. It has special wetting properties, has important characteristics such as waterproof, anti-fog, anti-cleaning, and anti-oxidation. It has broad application prospects in many fields such as scientific research, production, and life, such as lenses, optical devices, textiles, and mechanical products. , pipeline transportation, microfluidic chips, etc. This type of special property can reduce the adhesion and friction of the device surface and improve the flow performance of liquid in the microfluidic device. Yasuhisa Ando of the Mechanical Engineering Laboratory of the University of Tsukuba in Japan published in Sensors and Actuators, Vol.57No.2 (1996), p, 83-89 and V.Studer of France published in AppI.Phys.Lett.80, 3614 (2002) The application of superhydrophobic surfaces was tentatively studied in the thesis. There are two main methods for superhydrophobic modification of the surface of solid materials: one is to construct rough micro-nano structures on the hydrophobic surface with a contact angle greater than 90°; the other is to modify the surface with low surface energy substances, such as Jiang Lei Published in Adv. Mater. 2002, 14: 1857-180 explained. There have also been some reports on the hydrophobic modification of solid surfaces combining the above two methods. For example (Chinese patents, publication numbers CN1378581A, CN1613565A, CN1624062A), Langmuir2008, 24, 10421-10426. However, some of the above-mentioned methods for constructing superhydrophobic surfaces generally have complicated processes and require special instruments and equipment, making it difficult to realize large-scale preparation. Therefore, it is more valuable to explore new and cheap superhydrophobic preparation technologies.
由于普通平面基底具有很高的反射率,致使光学系统受到杂光干扰,严重地影响光学系统中光学元件的透过率和图像解析能力,致使光学系统的分辨率和灵敏度下降,严重地影响了光学及光电子学器件的性能,例如太阳能电池、显示器、光学传感器、偏振片、光学镜头等。为了提高这些器件的性能,需要降低基底表面对光的反射率。传统构筑抗反射亚波长表面结构的方法主要有:电子束刻蚀、基于纳米压印的干刻刻蚀、激光干涉刻蚀等。为了构筑抗反射表面,科技工作者进行了大量的研究工作,其中最具影响力的是电子束刻蚀的方法(Opt.Lett.1999,24,1422;Microeletron.Eng.2005,78~79,287)。虽然电子束刻蚀的方法具有高精度、高分辨率等优点,但是由于仪器昂贵、效率较低的缺点,制约了其广泛的应用。基于和自组装纳米粒子的方法制备的结构、激光干涉刻蚀和纳米压印的掩模,RIE能够在大面积上构筑出具有抗反射性能的亚波长结构(Nanotechnology 2000.11.161;Nanotechnology 1997.8.53;AppI.Phys.Lett.2002.80.2242;J.Vac.Sci.Tehchnol.2003.21.287 4Small 2008.4.1972中国专利,公开号CN1378581A,CN1613565 A,CN1624062 A),然而这些技术需要的仪器依旧很昂贵,使其应用严重受限。Due to the high reflectivity of ordinary planar substrates, the optical system is disturbed by stray light, which seriously affects the transmittance and image resolution capabilities of the optical components in the optical system, resulting in a decrease in the resolution and sensitivity of the optical system, which seriously affects the Performance of optical and optoelectronic devices, such as solar cells, displays, optical sensors, polarizers, optical lenses, etc. In order to improve the performance of these devices, it is necessary to reduce the reflectivity of the substrate surface to light. Traditional methods for constructing anti-reflective subwavelength surface structures mainly include: electron beam etching, dry etching based on nanoimprinting, laser interference etching, etc. In order to build anti-reflection surfaces, scientific and technological workers have carried out a lot of research work, the most influential of which is the method of electron beam etching (Opt.Lett.1999, 24, 1422; Microeletron.Eng.2005, 78~79,287) . Although the method of electron beam etching has the advantages of high precision and high resolution, its wide application is restricted due to the disadvantages of expensive equipment and low efficiency. Based on the structure prepared by the self-assembled nanoparticle method, laser interference etching and nanoimprinting mask, RIE can construct a sub-wavelength structure with anti-reflection properties on a large area (Nanotechnology 2000.11.161; Nanotechnology 1997.8.53 ; AppI.Phys.Lett.2002.80.2242; J.Vac.Sci.Tehchnol.2003.21.287 4Small 2008.4.1972 Chinese patent, publication number CN1378581A, CN1613565 A, CN1624062 A), but the instrument that these technologies need is still very expensive, Its application is severely limited.
发明内容 Contents of the invention
本发明的目的在于以一种简单的方法来制备大面积的超疏水抗反射硅表面,提出的是一种具有微米和纳米复合结构的超疏水抗反射硅表面的制备方法。本发明是利用单晶硅在碱性溶液中的各向异性刻蚀作用及银催化刻蚀硅法制备出表面微观结构为微米和纳米结构共同存在的复合结构,再通过含氟代硅烷化试剂对其表面进行化学修饰,制备的硅表面同时具有良好的超疏水和抗反射性能。运用该方法制备的超疏水抗反射材料的表面与水的静态接触角大于150°,如图7水滴在此表面上的滑动角小于3°(静态接触角和滚动角均在contact angle OCA20.DATAPHYSICS上测试)。此表面还具有良好的抗反射性能,尤其在800~1100nm波长范围内光反射率小于3%。The purpose of the present invention is to prepare a large-area super-hydrophobic anti-reflective silicon surface in a simple method, and proposes a method for preparing a super-hydrophobic anti-reflective silicon surface with a micron and nanocomposite structure. The present invention utilizes the anisotropic etching effect of single crystal silicon in alkaline solution and the silver-catalyzed silicon etching method to prepare a composite structure in which the surface microstructure is co-existed with micron and nanostructures, and then through the fluorine-containing silylating agent The surface is chemically modified, and the prepared silicon surface has good superhydrophobic and antireflection properties at the same time. The static contact angle between the surface of the superhydrophobic anti-reflective material prepared by this method and water is greater than 150°, as shown in Figure 7, the sliding angle of water droplets on this surface is less than 3° (both the static contact angle and the rolling angle are within contact angle OCA20.DATAPHYSICS on the test). The surface also has good anti-reflection performance, especially the light reflectance is less than 3% in the wavelength range of 800-1100nm.
本发明所述的方法具有操作简单、普适性好、成本低廉、大面积、快速高效等优点,为拓展硅材料在工业生产中的应用提供了一种新的制备途径,可规模化生产微纳复合结构的超疏水抗反射硅表面,可以广泛的应用于太阳能电池、微流体芯片、光电器件等方面,具有良好的工业应用前景。The method of the present invention has the advantages of simple operation, good universality, low cost, large area, fast and high efficiency, etc., and provides a new preparation method for expanding the application of silicon materials in industrial production, and can produce micro The superhydrophobic anti-reflective silicon surface of the nanocomposite structure can be widely used in solar cells, microfluidic chips, optoelectronic devices, etc., and has good industrial application prospects.
为了实现制备超疏水抗反射微米纳米复合结构硅表面,本发明采用的方案是在硅表面依次构筑微米和纳米结构,其中微米级硅岛或网格(光刻方法得到为网格结构)的高度为1~7μm,纳米孔洞的直径约为80~140nm。In order to realize the preparation of superhydrophobic anti-reflection micro-nano composite structure silicon surface, the scheme adopted in the present invention is to build micron and nanostructures on the silicon surface successively, wherein the height of micron-scale silicon islands or grids (obtained as a grid structure by photolithography method) The diameter of the nanohole is about 80-140nm.
本发明所述的制备微米和纳米复合结构的超疏水抗反射硅表面的方法,包括如下步骤:The method for preparing the superhydrophobic anti-reflection silicon surface of the micron and nanocomposite structure of the present invention, comprises the steps:
(1)选取n-100、p-100、n-111、p-111等晶型的硅片,并对其表面进行清洁处理,处理的过程为:将硅片分别在丙酮、氯仿、乙醇、水中进行超声清洗,超声功率为50~150W,时间1~10min,然后将硅片放入到质量分数为1~10%的HF溶液中5~10min,除去表面的二氧化硅,最后用去离子水清洗,然后用高纯氮气吹干;(1) Select silicon wafers of n-100, p-100, n-111, p-111 and other crystal forms, and clean the surface. Ultrasonic cleaning in water, the ultrasonic power is 50-150W, the time is 1-10min, and then the silicon wafer is put into the HF solution with a mass fraction of 1-10% for 5-10min to remove the silicon dioxide on the surface, and finally deionized Wash with water, then blow dry with high-purity nitrogen;
(2)通过碱溶液刻蚀、RIE刻蚀、光刻或纳米压印的方法,在硅片的表面形成微米级硅岛或网格;(2) Form micron-scale silicon islands or grids on the surface of the silicon wafer by alkaline solution etching, RIE etching, photolithography or nanoimprinting;
上述方法中所述的碱溶液刻蚀的方法,是将清洁后的硅片放入pH为10~14的40℃~110℃ KOH、NaOH、EDP(乙二胺、邻苯二酚和水的混合溶液)和氨水溶液中0.5~3h,由于碱性溶液对硅的各向异性刻蚀作用,从而在硅表面制备了微米级硅岛,硅岛的高度为5~7μm;The method of alkali solution etching described in the above-mentioned method is to put the silicon chip after cleaning into
上述方法中所述的RIE刻蚀的方法,是将水面上单层紧密六方堆积的PS球的阵列转移到清洁后的硅表面上,然后将得到的样品通过RIE刻蚀来制备硅岛微结构,刻蚀的气体为SF6(20~45sccm)和CHF3(3~12sccm),刻蚀的功率80~160W,腔体压力25~60mTorr,刻蚀时间300~1000s,得到的微米级硅岛,其扫描电镜照片如图4所示,硅岛的高度为1.0~3.0μm。The RIE etching method described in the above method is to transfer the array of PS spheres with a single layer of close hexagonal packing on the water surface to the cleaned silicon surface, and then use the obtained sample to prepare the silicon island microstructure by RIE etching. , the etching gas is SF 6 (20-45sccm) and CHF 3 (3-12sccm), the etching power is 80-160W, the chamber pressure is 25-60mTorr, and the etching time is 300-1000s. The obtained micron-sized silicon islands , the scanning electron microscope photo is shown in Figure 4, the height of the silicon island is 1.0 ~ 3.0 μm.
上述方法中所述的光刻的方法,是选用清洁后的硅片作为基底材料,在使用之前经氧等离子体系统处理2~8min,使表面清洁而且亲水,便于光刻胶的旋涂成膜。旋涂光刻胶的条件为:1000~2500转/S,旋转15~60S,旋涂完毕后将样品在80~100℃条件下淬火25~45min。然后在掩模曝光机下控制曝光电流3.5A,曝光40s,曝光完毕在显影液(BP~212紫外正型光刻胶显影液)中显影1-3s,放入蒸馏水中洗净残留的显影液,用氮气吹干,即得光刻胶微米网格结构,微结构周期10μm,孔洞5μm,条带宽度5μm。然后将得到的样品通过RIE刻蚀来制备微米级硅网格结构,刻蚀的气体为SF6(20~45sccm)和CHF3(3~12sccm),刻蚀的功率80~160W,腔体压力25~60mTorr,刻蚀时间600~1500s,制备的微米级硅网格的高度为3~6μm。The photolithography method described in the above method is to select the cleaned silicon wafer as the base material, and process it through an oxygen plasma system for 2 to 8 minutes before use to make the surface clean and hydrophilic, which is convenient for the spin coating of the photoresist. membrane. The conditions for spin-coating the photoresist are: 1000-2500 revolutions/S, spin for 15-60S, and quench the sample at 80-100° C. for 25-45 minutes after the spin-coating is completed. Then control the exposure current 3.5A under the mask exposure machine, expose for 40s, develop in the developer solution (BP~212 UV positive photoresist developer) for 1-3s after exposure, and wash the remaining developer solution in distilled water , blown dry with nitrogen to obtain a photoresist micro-grid structure with a microstructure period of 10 μm, a hole of 5 μm, and a strip width of 5 μm. Then the obtained sample is etched by RIE to prepare a micron-scale silicon grid structure, the etching gas is SF 6 (20-45 sccm) and CHF 3 (3-12 sccm), the etching power is 80-160W, and the chamber pressure 25-60 mTorr, the etching time is 600-1500 s, and the height of the prepared micron-scale silicon grid is 3-6 μm.
上述方法中所述的纳米压印的方法,是取少量热塑型高分子聚合物MRI~7030(Micro Resist公司,德国)或聚甲基丙烯酸甲酯PMMA旋涂于清洁后的硅片表面上,旋涂厚度约为200~500nm,利用瑞典的OBDUCAT公司生产的2.5英寸纳米压印机,以氮化硅材料的模板(通过电子束刻蚀的方法构筑,点阵型结构,其点的大小尺寸范围为800nm×800nm~10μm×10μm,点的间距尺寸范围为800nm~10μm)构筑出高分子与模板结构互补的有序结构,即利用纳米压印的方法在基底表面构筑微米级结构。然后利用氧等离子体去掉点阵间的聚合物层,露出硅片表面,然后将得到的样品以点阵结构的聚合物为阻挡层通过RIE刻蚀来制备微米级硅岛,刻蚀的气体为SF6(20~45sccm)和CHF3(3~12sccm),刻蚀的功率80~160W,腔体压力25~60mTorr,刻蚀时间500~1500s,得到的硅岛的高度为2~4.5μm。The method for nanoimprinting described in the above-mentioned method is to get a small amount of thermoplastic polymer MRI~7030 (Micro Resist company, Germany) or polymethyl methacrylate PMMA to spin-coat on the silicon chip surface after cleaning , the spin-coating thickness is about 200-500nm, using a 2.5-inch nano-imprinting machine produced by Sweden's OBDUCAT company, using a template of silicon nitride material (constructed by electron beam etching, a lattice structure, the size of the dots The range is 800nm×800nm~10μm×10μm, and the pitch size of the dots ranges from 800nm~10μm) to build an ordered structure complementary to the polymer and template structure, that is, to use the nanoimprint method to build a micron-scale structure on the surface of the substrate. Then use oxygen plasma to remove the polymer layer between the lattices to expose the surface of the silicon wafer, and then use the polymer of the lattice structure as a barrier layer to prepare micron-scale silicon islands by RIE etching with the obtained sample. The etching gas is For SF 6 (20-45sccm) and CHF 3 (3-12sccm), the etching power is 80-160W, the chamber pressure is 25-60mTorr, the etching time is 500-1500s, and the height of the obtained silicon island is 2-4.5μm.
(3)通过无电沉积、电沉积或化学气相沉积的方法,将金或银纳米离子沉积在微米级硅岛或网格结构的表面,沉积的金或银纳米粒子的厚度为5~15nm;然后将微米级硅岛或网格结构表面的硅片放入到HF/H2O2/H2O溶液中(质量分数为40~60%的HF、质量分数为20~40%的H2O2、H2O的体积比为1~3:5~8:10~15,进行催化刻蚀,进而制备纳米级孔洞,最后用质量分数为30~50%的硝酸浸泡5~10min将银或金纳米粒子洗去,进而得到复米和纳米复合结构的表面;(3) Deposit gold or silver nano ions on the surface of micron-scale silicon islands or grid structures by electroless deposition, electrodeposition or chemical vapor deposition, and the thickness of the deposited gold or silver nanoparticles is 5-15 nm; Then put the micron-scale silicon island or the silicon chip on the surface of the grid structure into the HF/H 2 O 2 /H 2 O solution (the mass fraction is 40-60% HF, the mass fraction is 20-40% H 2 The volume ratio of O 2 and H 2 O is 1-3:5-8:10-15, and the catalytic etching is carried out to prepare nano-scale holes. Or gold nanoparticles are washed away, and then the surface of complex rice and nanocomposite structure is obtained;
上述方法中所述的无电沉积的方法,是将表面制备了微米级硅岛或网格的硅片放入到4~5M的HF和0.01~0.02MAgNO3的混合溶液中,无电沉积银纳米粒子,沉积时间为1~4min;The electroless deposition method described in the above method is to put the silicon chip with micron-scale silicon islands or grids on the surface into the mixed solution of 4~5M HF and 0.01~ 0.02MAgNO3 , and electrolessly deposit silver For nanoparticles, the deposition time is 1 to 4 minutes;
上述方法中所述的电沉积的方法,是将表面制备了微米级硅岛或网格的硅片放入到0.01~0.05M的电解液AgNO3中,沉积电压为400~800mv,沉积时间为10~20min;或将表面制备了微米级硅岛或网格的硅片放入到0.01~0.05M的电解液氯金酸中,沉积电压为500~700mv,沉积时间为8~20min;The method of electrodeposition described in the above method is to put the silicon wafer with micron-scale silicon islands or grids on the surface into the electrolyte solution AgNO3 of 0.01-0.05M, the deposition voltage is 400-800mv, and the deposition time is 10-20min; or put the silicon wafer with micron-scale silicon islands or grids on the surface into the 0.01-0.05M electrolyte chloroauric acid, the deposition voltage is 500-700mv, and the deposition time is 8-20min;
(4)对已制备的微米和纳米级结构的表面进行化学修饰:将得到的微米和纳米复合结构表面的硅片放入干净的玻璃培养皿中,在培养皿底部滴0.5~1.0ml氟代硅烷化试剂,如十七氟癸基三甲氧基硅烷、全氟辛烷磺酸(PFOS),全氟癸基三乙氧基硅烷(PFDTES)、十二烷基三氯硅烷(DTS)、十八烷基三氯硅烷(ODTS)、全氟辛基甲基二氯硅烷(TFPS)等,加热到100~350℃保持1~3.5h,然后冷却到室温,这样就得到具有微米和纳米复合结构的超疏水抗反射硅表面。(4) Chemically modify the surface of the prepared micro- and nano-scale structures: put the obtained silicon wafers on the surface of the micro- and nano-composite structures into a clean glass petri dish, drop 0.5 to 1.0 ml of fluoride on the bottom of the petri dish Silylating agents, such as heptadecylfluorodecyltrimethoxysilane, perfluorooctanesulfonic acid (PFOS), perfluorodecyltriethoxysilane (PFDTES), dodecyltrichlorosilane (DTS), Octalkyltrichlorosilane (ODTS), perfluorooctylmethyldichlorosilane (TFPS), etc., heated to 100-350°C for 1-3.5h, and then cooled to room temperature, so that micro and nano composite structures can be obtained superhydrophobic antireflective silicon surface.
本发明所制备的微米纳米复合结构的超疏水抗反射硅表面,有许多优点和良好的用途。The super-hydrophobic anti-reflection silicon surface of the micro-nano composite structure prepared by the invention has many advantages and good applications.
(1)本方法工艺简单、廉价,普适性很强,易于生产;(1) The process of the method is simple, cheap, highly universal and easy to produce;
(2)本发明无需任何模板,能够实现大面积的制备,参见图9。(2) The present invention does not require any template, and can realize large-area preparation, see FIG. 9 .
(3)本发明的微米纳米复合结构表面具有非常大的接触角(大于150°),以及很小的接触角滞后(小于3°),水珠在上面滚动能带走表面的灰尘实现自清洁;(3) The surface of the micro-nano composite structure of the present invention has a very large contact angle (greater than 150°), and a very small contact angle hysteresis (less than 3°), and the dust on the surface can be taken away by water droplets to realize self-cleaning ;
(4)超疏水表面具有不粘水,自清洁的功能,可以用于微电子微机械系统中的一些减阻原件,以减小噪音和减小摩擦及防止腐蚀;(4) The super-hydrophobic surface has the function of non-stick water and self-cleaning, and can be used in some drag-reducing components in microelectronic and micro-mechanical systems to reduce noise, reduce friction and prevent corrosion;
(5)低的表面能和超疏水特性,能够降低微流通道沿程压力损失,增加流体的流动速度,可用于微流体芯片中的无损失超微量液体的输送;(5) Low surface energy and super-hydrophobic properties can reduce the pressure loss along the microfluidic channel, increase the flow velocity of the fluid, and can be used for the lossless delivery of ultra-micro liquid in the microfluidic chip;
(6)微米纳米复合结构的硅表面兼具有抗反射的性能,可以广泛应用于太阳能电池、光电器件等方面。(6) The silicon surface of the micro-nano composite structure has anti-reflection properties, and can be widely used in solar cells, optoelectronic devices, and the like.
附图说明 Description of drawings
图1:制备微米和纳米复合结构超疏水抗反射硅表面的工艺示意图;Figure 1: Schematic diagram of the process for preparing superhydrophobic anti-reflective silicon surfaces with micro- and nano-composite structures;
图2:制备的硅岛结构的SEM图片;Figure 2: SEM picture of the prepared silicon island structure;
图3:单层排列在硅片表面的直径为1.1μm的PS球的SEM图片;Figure 3: SEM image of PS spheres with a diameter of 1.1 μm arranged in a single layer on the surface of a silicon wafer;
图4:以直径为1.1μm的PS球做档层,RIE刻蚀硅得到的硅岛的SEM图片;Figure 4: SEM images of silicon islands obtained by RIE etching silicon with PS balls with a diameter of 1.1 μm as the barrier layer;
图5:硅岛表面无电沉积银纳米粒子后的SEM图片;Figure 5: SEM image after electroless deposition of silver nanoparticles on the surface of the silicon island;
图6:制备的微纳米复合结构的SEM图片;Figure 6: SEM picture of the prepared micro-nano composite structure;
图7:测量接触角的CCD照片;Figure 7: CCD photo for measuring contact angle;
图8:反射光谱曲线;Figure 8: Reflectance spectrum curve;
图9:所制备的大面积微米纳米复合结构的超疏水抗反射硅表面的数码相机照片(右)和相应硅片的对比照片(左)。Figure 9: A digital camera photo (right) of the prepared superhydrophobic antireflective silicon surface of a large-area micro-nano composite structure and a comparative photo of the corresponding silicon wafer (left).
如图1所示,首先选取n-100型硅片,并对其表面进行清洁处理。然后将其放入pH为14、60℃、KOH溶液中1h,得到硅表面的微米硅岛结构。然后在硅岛结构的表面沉积金或银纳米粒子。最后,通过金或银的催化刻蚀制备微米和纳米的复合结构。As shown in Figure 1, the n-100 type silicon wafer is first selected, and its surface is cleaned. Then put it into a KOH solution with a pH of 14 and 60° C. for 1 hour to obtain a micron silicon island structure on the silicon surface. Gold or silver nanoparticles are then deposited on the surface of the silicon island structures. Finally, micro- and nano-composite structures are prepared by catalytic etching of gold or silver.
如图2所示,为制备的硅岛结构,硅岛的底边边长为4~6μm,高度为5~7μm。具体制备过程参见实施例1As shown in FIG. 2 , the prepared silicon island structure has a bottom side length of 4-6 μm and a height of 5-7 μm. Concrete preparation process is referring to
如图3所示,将水面上单层PS球转移到硅表面上,用扫描电子显微镜来检测PS球的阵列,从SEM图中可以看出,我们制备得到紧密六方堆积的PS球的阵列结构。具体过程参见实施例6。As shown in Figure 3, the single layer of PS spheres on the water surface was transferred to the silicon surface, and the array of PS spheres was detected by a scanning electron microscope. It can be seen from the SEM image that we have prepared an array structure of closely packed hexagonal PS spheres . See embodiment 6 for the specific process.
如图4所示,将得到的直径为1.1μm的PS球单层排列在硅片表面的样品通过RIE刻蚀来制备硅岛微结构,刻蚀的气体为SF6(30sccm)和CHF3(6sccm)(SF6:CHF3=5:1),刻蚀的功率100W,腔体压力30mTorr,刻蚀时间为710s。具体过程参见实施例6。As shown in Figure 4, the obtained sample with a diameter of 1.1 μm PS spheres arranged in a single layer on the surface of a silicon wafer was etched by RIE to prepare a silicon island microstructure, and the etching gas was SF 6 (30 sccm) and CHF 3 ( 6 sccm) (SF 6 :CHF 3 =5:1), the etching power is 100W, the cavity pressure is 30mTorr, and the etching time is 710s. See embodiment 6 for the specific process.
如图5所示,在硅岛的表面均匀的沉积上了一层金属银的纳米粒子,纳米粒子的粒径为100nm左右,因此,下一步催化刻蚀所得到的纳米孔洞的尺寸也为100nm左右。图片中显示了两个硅岛,右下角为其中一个硅岛的岛尖部分,后面的为硅岛的一个侧面,可以看出上面均匀的沉积了一层纳米粒子。具体过程参见实施例1。As shown in Figure 5, a layer of metal silver nanoparticles is evenly deposited on the surface of the silicon island, and the particle size of the nanoparticles is about 100nm. Therefore, the size of the nanopores obtained by the next step of catalytic etching is also 100nm. about. The picture shows two silicon islands. The lower right corner is the tip of one of the silicon islands, and the back is a side of the silicon island. It can be seen that a layer of nanoparticles is evenly deposited on it. See
如图6所示,为制备的微米和纳米复合结构,我们可以看出刻蚀之后微米岛的结构保持完好,并且通过刻蚀在岛的表面制备出100nm左右的纳米孔洞结构,实现了微纳复合结构。具体过程参见实施例1。As shown in Figure 6, for the prepared micro-nano composite structure, we can see that the structure of the micro-island remains intact after etching, and a nano-hole structure of about 100nm is prepared on the surface of the island by etching, realizing the realization of micro-nano Composite structure. See
如图7所示,接触角的CCD照片中,水滴的边缘轮廓不是很清晰,原因是因为制备结构的滚动角很小,水滴在滚动,这也说明我们制备的的结构有很好的超疏水效果。具体过程参见实施例1。As shown in Figure 7, in the CCD photo of the contact angle, the edge profile of the water droplet is not very clear, because the rolling angle of the prepared structure is very small, and the water droplet is rolling, which also shows that the structure we prepared has very good superhydrophobicity Effect. See
如图8所示,为反射光谱曲线,曲线a为在无硅岛结构的硅片表面直接沉积银纳米粒子,然后催化刻蚀得到的纳米级结构的反射光谱曲线。曲线b为我们制备的微纳米复合结构的反射光谱曲线,在测量的整个波长范围内都有很好的抗反射效果,尤其是在800~1100nm波长内,其反射率低于3%。曲线c为纯硅片的反射光谱曲线,其反射率在40%。曲线d为硅岛结构的反射光谱曲线。具体过程参见实施例1。As shown in FIG. 8 , it is a reflection spectrum curve, and curve a is the reflection spectrum curve of a nanoscale structure obtained by directly depositing silver nanoparticles on the surface of a silicon wafer without a silicon island structure, and then catalytically etching. Curve b is the reflection spectrum curve of the micro-nano composite structure prepared by us, which has good anti-reflection effect in the entire measured wavelength range, especially in the wavelength range of 800-1100nm, and its reflectance is lower than 3%. Curve c is the reflectance spectrum curve of a pure silicon wafer, and its reflectivity is 40%. Curve d is the reflection spectrum curve of the silicon island structure. See
如图9所示,为在整个硅片上制备的微纳米复合结构的数码相机照片,从照片上可以看出我们的结构上并没有大的缺陷,适合大面积加工。As shown in Figure 9, it is a digital camera photo of the micro-nano composite structure prepared on the entire silicon wafer. It can be seen from the photo that our structure has no major defects and is suitable for large-area processing.
具体实施方式 Detailed ways
实施例1:Example 1:
(1)选取n-100型硅片,并对其表面进行清洁处理。处理的过程为:将硅片分别在丙酮、氯仿、乙醇、水中进行超声清洗,超声功率为100W,时间5min。然后将硅片放入到质量分数为1%的HF溶液中5min,除去表面的二氧化硅,最后用去离子水清洗,高纯氮气吹干。(1) Select n-100 type silicon wafer and clean its surface. The treatment process is as follows: ultrasonically clean the silicon wafer in acetone, chloroform, ethanol, and water respectively, with an ultrasonic power of 100W for 5 minutes. Then put the silicon chip into the HF solution with a mass fraction of 1% for 5 minutes to remove the silicon dioxide on the surface, and finally wash it with deionized water and dry it with high-purity nitrogen gas.
(2)在硅表面制备微米级硅岛结构,过程如下:将已进行清洁处理的硅片放入pH为14的60℃的KOH溶液中1h,在碱性溶液中硅被各向异性刻蚀,从而制备了硅表面的硅岛结构,硅岛的底边边长为4~6μm,高度为5~7μm。如图2所示。(2) Prepare micron-scale silicon island structures on the silicon surface. The process is as follows: put the cleaned silicon wafer into a KOH solution at 60°C with a pH of 14 for 1 hour, and silicon is etched anisotropically in the alkaline solution. , thereby preparing a silicon island structure on the silicon surface, the bottom side of the silicon island is 4-6 μm long, and the height is 5-7 μm. as shown in picture 2.
(3)在微米级硅岛的表面制备纳米级孔洞,首先将表面制备了硅岛的硅片放入到4.6M的HF和0.01M的AgNO3的混合溶液中,无电沉积银纳米粒子1分钟,如图5所示。然后将表面长有银纳米粒子的硅岛结构放入到HF/H2O2/H2O的混合溶液中(质量分数为的49%HF,质量分数为30%的H2O2,和H2O的体积比为1:5:10),进行催化刻蚀30s,以制备纳米级孔洞。最后用质量分数为30%硝酸浸泡5min将银纳米粒子洗去,如图6所示。(3) To prepare nanoscale pores on the surface of micron-scale silicon islands, first place the silicon wafer with silicon islands on the surface into a mixed solution of 4.6M HF and 0.01M AgNO3 , and electrolessly
(4)对已制备的结构表面进行化学修饰,将得到的微米纳米复合结构放入干净的玻璃培养皿中,在培养皿底部滴0.5ml的十七氟癸基三甲氧基硅烷,加热到250℃,保持2.5h,然后冷却到室温。测得表面的接触角为156°,如图7。反射率低于5%,如图8。(4) Chemically modify the surface of the prepared structure, put the obtained micro-nano composite structure into a clean glass petri dish, drop 0.5ml of heptadecafluorodecyltrimethoxysilane at the bottom of the petri dish, heat to 250 ℃, keep 2.5h, then cool to room temperature. The measured surface contact angle is 156°, as shown in Figure 7. The reflectivity is lower than 5%, as shown in Figure 8.
实施例2:Example 2:
按实施例1的方法与步骤,将无电沉积银纳米粒子改为电沉积,电解液为0.01M的AgNO3溶液,沉积电压为400mv,沉积时间为15min,其他步骤同实施例1,同样可以得到超疏水抗反射硅表面,制备结构的硅岛高度为5~7μm,纳米级孔洞的大小约为130纳米,接触角为153°,反射率低于8%。According to the method and steps of Example 1, the electroless deposition of silver nanoparticles is changed to electrodeposition, the electrolyte is 0.01M AgNO solution, the deposition voltage is 400mv, and the deposition time is 15min. Other steps are the same as in Example 1, and can be The super-hydrophobic anti-reflective silicon surface is obtained, the height of the silicon island of the prepared structure is 5-7 μm, the size of the nanoscale hole is about 130 nanometers, the contact angle is 153°, and the reflectivity is lower than 8%.
实施例3:Example 3:
按实施例1的方法与步骤,将无电沉积银纳米粒子改为电沉积金纳米粒子,电解液为0.01M的氯金酸溶液,沉积电压为500mv,沉积时间为10min,其他步骤同实施例1,同样可以得到超疏水抗反射硅表面,制备结构的硅岛高度为5~7μm,纳米级孔洞的大小约为120纳米,接触角为150°,反射率低于8%。According to the method and steps of Example 1, the electroless deposition of silver nanoparticles is changed to electrodeposition of gold nanoparticles, the electrolyte is 0.01M chloroauric acid solution, the deposition voltage is 500mv, and the deposition time is 10min. Other steps are the same as in the embodiment. 1. The superhydrophobic anti-reflective silicon surface can also be obtained. The height of the silicon island of the prepared structure is 5-7 μm, the size of the nanoscale hole is about 120 nanometers, the contact angle is 150°, and the reflectivity is lower than 8%.
实施例4:Example 4:
按实施例1的方法与步骤,将无电沉积银纳米粒子改为化学气相沉积,沉积银纳米粒子的厚度为5nm,其他步骤同实施例1,同样可以得到超疏水抗反射硅表面。制备结构的硅岛高度为5~7μm,纳米级孔洞的大小约为100纳米,接触角为157°,反射率低于6%。According to the method and steps of Example 1, the electroless deposition of silver nanoparticles is changed to chemical vapor deposition, and the thickness of the deposited silver nanoparticles is 5nm. Other steps are the same as in Example 1, and a superhydrophobic antireflective silicon surface can also be obtained. The height of the silicon island of the prepared structure is 5-7 μm, the size of the nanoscale holes is about 100 nanometers, the contact angle is 157°, and the reflectivity is lower than 6%.
实施例5:Example 5:
按实施例1的方法与步骤,将无电沉积银纳米粒子改为化学气相沉积金纳米粒子,沉积金纳米粒子的厚度为5nm,其他步骤同实施例1,同样可以得到超疏水抗反射硅表面。制备结构的硅岛高度为5~7μm,纳米级孔洞的大小约为100纳米,接触角为158°,反射率低于6%。According to the method and steps of Example 1, the electroless deposition of silver nanoparticles is changed to chemical vapor deposition of gold nanoparticles, and the thickness of the deposited gold nanoparticles is 5nm. The other steps are the same as in Example 1, and the superhydrophobic antireflection silicon surface can also be obtained. . The height of the silicon island of the prepared structure is 5-7 μm, the size of the nanoscale holes is about 100 nanometers, the contact angle is 158°, and the reflectivity is lower than 6%.
实施例6:Embodiment 6:
(1)选取n-100型硅片,并对其表面进行清洁处理。处理的过程为:将硅片分别在丙酮、氯仿、乙醇、水中进行超声清洗,超声功率为100W,时间5min。然后将硅片放入到1%的HF溶液中5min,除去表面的二氧化硅,最后用去离子水清洗,高纯氮气吹干。(1) Select n-100 type silicon wafer and clean its surface. The treatment process is as follows: ultrasonically clean the silicon wafer in acetone, chloroform, ethanol, and water respectively, with an ultrasonic power of 100W for 5 minutes. Then put the silicon chip into 1% HF solution for 5 minutes to remove the silicon dioxide on the surface, and finally wash it with deionized water and dry it with high-purity nitrogen gas.
(2)在硅表面制备微米级硅岛结构,过程如下:从Microparticles GmbH(Germany)处购买质量分数为10%的PS溶液,以等体积与乙醇混合,超生15min待用。在直径为15cm的玻璃培养皿中加入150mL高纯水(经法国MILLI~Q超纯水仪处理,电阻率为18.2MΩcm),取5μL制备好的溶液滴到硅片上,这时PS微球在水面分散开形成无序的结构,等待50min后加入5μL2%的十二烷基硫酸钠溶液,这时PS球就会在水面上形成有序的单层阵列,将水面上单层PS球转移到硅表面上,用扫描电镜来检测PS球的阵列,如图3所示。从电镜图中可以看出,我们制备得到紧密六方堆积的PS球的阵列结构。然后将得到的样品通过RIE刻蚀来制备硅岛微结构,刻蚀的气体为SF6(30sccm)和CHF3(6sccm)(SF6:CHF3=5:1),刻蚀的功率100W,腔体压力30mTorr,刻蚀时间380s,得到的硅岛微结构的扫描电镜图片如图4所示。制备结构的硅岛高度为1μm。(2) Preparation of micron-scale silicon island structures on the silicon surface, the process is as follows: buy a PS solution with a mass fraction of 10% from Microparticles GmbH (Germany), mix it with ethanol in equal volume, and supercharge for 15 minutes before use. Add 150mL of high-purity water (treated by a French MILLI~Q ultrapure water instrument, with a resistivity of 18.2MΩcm) into a glass petri dish with a diameter of 15cm, and take 5μL of the prepared solution and drop it on the silicon wafer. At this time, the PS microspheres are on the water surface. Disperse to form a disordered structure, wait for 50min and add 5 μL of 2% sodium dodecyl sulfate solution, then the PS balls will form an ordered monolayer array on the water surface, transfer the monolayer PS balls on the water surface to silicon On the surface, a scanning electron microscope was used to examine the array of PS spheres, as shown in Figure 3. It can be seen from the electron microscope images that we have prepared an array structure of closely packed hexagonal PS spheres. Then the obtained sample was etched by RIE to prepare the silicon island microstructure, the etching gas was SF 6 (30 sccm) and CHF 3 (6 sccm) (SF 6 :CHF 3 =5:1), the etching power was 100W, The cavity pressure is 30mTorr, and the etching time is 380s. The scanning electron microscope picture of the obtained silicon island microstructure is shown in FIG. 4 . The silicon island height of the fabricated structure was 1 μm.
(3)在微米级的硅岛表面制备纳米级孔洞,首先将表面制备了硅岛的硅片放入到4.6M的HF和0.01M的AgNO3的混合溶液中,无电沉积银纳米粒子1min,然后,将表面长有银纳米粒子的硅岛结构放入到HF/H2O2/H2O溶液中(质量分数分别为49%HF,30%H2O2和H2O的体积比为1:5:10),进行催化刻蚀30s,以制备纳米级孔洞,最后用质量分数为30%的硝酸浸泡5min将银纳米粒子洗去。(3) To prepare nanoscale pores on the surface of micron-scale silicon islands, first put the silicon wafer with silicon islands on the surface into a mixed solution of 4.6M HF and 0.01M AgNO3 , and electrolessly deposit silver nanoparticles for 1min , and then put the silicon island structure with silver nanoparticles on the surface into the HF/H 2 O 2 /H 2 O solution (the mass fractions are respectively 49% HF, 30% H 2 O 2 and the volume of H 2 O The ratio is 1:5:10), and the catalytic etching is carried out for 30s to prepare nanoscale holes, and finally the silver nanoparticles are washed away by soaking in nitric acid with a mass fraction of 30% for 5min.
(4)对已制备的结构进行表面化学修饰,将得到的微米纳米复合结构放入干净的玻璃培养皿中,在培养皿底部滴0.5ml的十七氟癸基三甲氧基硅烷,加热到250℃,保持2.5h,然后冷却到室温。制备结构的硅岛高度为1μm,纳米级孔洞的大小约为100纳米,接触角大小为150°,反射率低于10%。(4) Carry out surface chemical modification to the prepared structure, put the obtained micro-nano composite structure into a clean glass petri dish, drop 0.5ml of heptadecafluorodecyltrimethoxysilane at the bottom of the petri dish, heat to 250 ℃, keep 2.5h, then cool to room temperature. The height of the silicon island of the prepared structure is 1 μm, the size of the nanoscale hole is about 100 nanometers, the size of the contact angle is 150°, and the reflectivity is lower than 10%.
实施例7:Embodiment 7:
按实施例6的方法与步骤,将无电沉积银纳米粒子改为电沉积,电解液为0.01M的AgNO3溶液,沉积电压为400mv,沉积时间为15min,其他步骤同实施例6,同样可以得到超疏水抗反射硅表面。制备结构的硅岛高度为1μm,纳米级孔洞的大小约为130纳米,接触角大小为151°,反射率低于10%。According to the method and steps of Example 6, the electroless deposition of silver nanoparticles is changed to electrodeposition, the electrolyte is 0.01M AgNO solution, the deposition voltage is 400mv, and the deposition time is 15min. Other steps are the same as in Example 6, and can be A superhydrophobic antireflective silicon surface is obtained. The height of the silicon island of the prepared structure is 1 μm, the size of the nanoscale hole is about 130 nanometers, the size of the contact angle is 151°, and the reflectivity is lower than 10%.
实施例8:Embodiment 8:
按实施例6的方法与步骤,将无电沉积银纳米粒子改为电沉积金纳米粒子,电解液为0.01M的氯金酸溶液,沉积电压为500mv,沉积时间为10min,其他步骤同实施例6,同样可以得到超疏水抗反射硅表面。制备结构的硅岛高度为1μm,纳米级孔洞的大小约为120纳米,接触角大小为152°,反射率低于10%。According to the method and steps of Example 6, the electroless deposition of silver nanoparticles is changed to electrodeposition of gold nanoparticles, the electrolyte is 0.01M chloroauric acid solution, the deposition voltage is 500mv, and the deposition time is 10min. Other steps are the same as in the embodiment. 6. It is also possible to obtain a super-hydrophobic anti-reflective silicon surface. The height of the silicon island of the prepared structure is 1 μm, the size of the nanoscale hole is about 120 nanometers, the size of the contact angle is 152°, and the reflectivity is lower than 10%.
实施例9:Embodiment 9:
按实施例6的方法与步骤,将无电沉积银纳米粒子改为化学气相沉积,沉积银纳米粒子的厚度为5nm,其他步骤同实施例6,同样可以得到超疏水抗反射硅表面。制备结构的硅岛高度为1μm,纳米级孔洞的大小约为100纳米,接触角大小为154°,反射率低于8%。According to the method and steps of Example 6, the electroless deposition of silver nanoparticles is changed to chemical vapor deposition, and the thickness of the deposited silver nanoparticles is 5nm. Other steps are the same as in Example 6, and a superhydrophobic antireflective silicon surface can also be obtained. The silicon island height of the prepared structure is 1 μm, the size of the nanoscale hole is about 100 nanometers, the contact angle is 154°, and the reflectivity is lower than 8%.
实施例10:Example 10:
按实施例6的方法与步骤,将无电沉积银纳米粒子改为化学气相沉积金纳米粒子,沉积金纳米粒子的厚度为5nm,其他步骤同实施例6,同样可以得到超疏水抗反射硅表面。制备结构的硅岛高度为1μm,纳米级孔洞的大小约为100纳米,接触角大小为153°,反射率低于8%。According to the method and steps of Example 6, the electroless deposition of silver nanoparticles is changed to chemical vapor deposition of gold nanoparticles, and the thickness of the deposited gold nanoparticles is 5nm. The other steps are the same as in Example 6, and the superhydrophobic anti-reflective silicon surface can also be obtained. . The silicon island height of the prepared structure is 1 μm, the size of the nanoscale holes is about 100 nanometers, the contact angle is 153°, and the reflectivity is lower than 8%.
实施例11:Example 11:
(1)选取n~100型硅片,并对其表面进行清洁处理。处理的过程为:将硅片分别在丙酮、氯仿、乙醇、水中进行超声清洗,超声功率为100W,时间5min。然后将硅片放入到1%的HF溶液中5min,除去表面的二氧化硅,最后用去离子水清洗,高纯氮气吹干。(1) Select n-100 type silicon wafers, and clean the surface. The treatment process is as follows: ultrasonically clean the silicon wafer in acetone, chloroform, ethanol, and water respectively, with an ultrasonic power of 100W for 5 minutes. Then put the silicon chip into 1% HF solution for 5 minutes to remove the silicon dioxide on the surface, and finally wash it with deionized water and dry it with high-purity nitrogen gas.
(2)在硅表面制备微米级硅网格结构,过程如下:选用上面清洁的硅片作为基底材料,在使用之前经氧等离子体系统处理5min,使表面清洁而且亲水,便于光刻胶的旋涂成膜。旋涂光刻胶的条件为:1500转/S,旋转15S,旋涂完毕后将样品在80℃条件下淬火30min。然后在掩模曝光机下控制曝光电流3.5A,曝光40s,曝光完毕在显影液(BP~212紫外正型光刻胶显影液)中显影3s,放入蒸馏水中洗净残留的显影液,用氮气吹干,即得光刻胶微米结构,微结构周期10μm,孔洞5μm,条带5μm。然后将得到的样品通过RIE刻蚀来制备硅网格微结构,刻蚀的气体为SF6(30sccm)和CHF3(6sccm)(SF6:CHF3=5:1),刻蚀的功率100W,腔体压力30mTorr,刻蚀时间900s,(2) Prepare a micron-scale silicon grid structure on the silicon surface. The process is as follows: select the silicon wafer cleaned above as the base material, and treat it with an oxygen plasma system for 5 minutes before use to make the surface clean and hydrophilic, which is convenient for the photoresist. Spin coating film. The conditions for spin-coating the photoresist are: 1500 rpm/S, spin for 15S, and quench the sample at 80° C. for 30 min after spin-coating. Then control the exposure current 3.5A under the mask exposure machine, expose for 40s, and develop for 3s in the developing solution (BP~212 ultraviolet positive photoresist developing solution) after exposure, put into distilled water to wash the remaining developing solution, and use Blow dry with nitrogen to obtain a photoresist microstructure with a microstructure period of 10 μm, a hole of 5 μm, and a strip of 5 μm. Then the obtained sample is etched by RIE to prepare a silicon grid microstructure, the etching gas is SF 6 (30 sccm) and CHF 3 (6 sccm) (SF 6 :CHF 3 =5:1), and the etching power is 100W , chamber pressure 30mTorr, etching time 900s,
(3)在微米级的硅网格结构的表面制备纳米级孔洞,首先将表面制备了硅网格的硅片放入到4.6M的HF和0.01M的AgNO3的混合溶液中,无电沉积银纳米粒子1分钟,然后,将表面长有银纳米粒子的硅网格结构放入到HF/H2O2/H2O溶液中(49%HF,30%H2O2和H2O的体积比为1:5:10),进行催化刻蚀30s,以制备纳米级孔洞。最后用硝酸将银纳米粒子洗去。(3) Prepare nanoscale pores on the surface of the micron-scale silicon grid structure. First, put the silicon wafer with the silicon grid on the surface into a mixed solution of 4.6M HF and 0.01M AgNO 3 for electroless deposition. silver nanoparticles for 1 minute, then put the silicon grid structure with silver nanoparticles on the surface into HF/H 2 O 2 /H 2 O solution (49% HF, 30% H 2 O 2 and H 2 O The volume ratio is 1:5:10), and the catalytic etching is carried out for 30s to prepare nanoscale holes. Finally, the silver nanoparticles were washed away with nitric acid.
(4)对已制备的结构进行表面化学修饰,将得到的微米纳米复合结构放入干净的玻璃培养皿中,在培养皿底部滴0.5ml的十七氟癸基三甲氧基硅烷,加热到250℃,保持2.5h,然后冷却到室温。制备结构的硅网格高度为3μm,纳米级孔洞的大小约为100纳米,接触角大小为155°,反射率低于7%。(4) Carry out surface chemical modification to the prepared structure, put the obtained micro-nano composite structure into a clean glass petri dish, drop 0.5ml of heptadecafluorodecyltrimethoxysilane at the bottom of the petri dish, heat to 250 ℃, keep 2.5h, then cool to room temperature. The silicon grid height of the prepared structure is 3 μm, the size of the nanoscale holes is about 100 nanometers, the contact angle is 155°, and the reflectivity is lower than 7%.
实施例12:Example 12:
按实施例11的方法与步骤,将无电沉积银纳米粒子改为电沉积,电解液为0.01M的AgNO3溶液,沉积电压为400mv,沉积时间为15min,其他步骤同实施例11,同样可以得到超疏水抗反射硅表面。制备结构的硅网格结构的高度为3μm,纳米级孔洞的大小约为130纳米,接触角大小为153°,反射率低于8%。According to the method and steps of Example 11, the electroless deposition of silver nanoparticles is changed to electrodeposition, the electrolyte is 0.01M AgNO solution, the deposition voltage is 400mv, and the deposition time is 15min. The other steps are the same as in Example 11. A superhydrophobic antireflective silicon surface is obtained. The height of the silicon grid structure of the prepared structure is 3 μm, the size of the nanoscale holes is about 130 nanometers, the size of the contact angle is 153°, and the reflectivity is lower than 8%.
实施例13:Example 13:
按实施例11的方法与步骤,将无电沉积银纳米粒子改为电沉积金纳米粒子,电解液为0.01M的氯金酸溶液,沉积电压为500mv,沉积时间为10min,其他步骤同实施例11,同样可以得到超疏水抗反射硅表面。制备结构的硅网格结构的高度为3μm,纳米级孔洞的大小约为120纳米,接触角大小为152°,反射率低于8%。According to the method and steps of Example 11, the electroless deposition of silver nanoparticles is changed to electrodeposition of gold nanoparticles, the electrolyte is 0.01M chloroauric acid solution, the deposition voltage is 500mv, and the deposition time is 10min. Other steps are the same as in the embodiment. 11. The superhydrophobic anti-reflection silicon surface can also be obtained. The height of the silicon grid structure of the prepared structure is 3 μm, the size of the nanoscale holes is about 120 nanometers, the size of the contact angle is 152°, and the reflectivity is lower than 8%.
实施例14:Example 14:
按实施例11的方法与步骤,将无电沉积银纳米粒子改为化学气相沉积,沉积银纳米粒子的厚度为5nm,其他步骤同实施例11,同样可以得到超疏水抗反射硅表面。制备结构的硅网格结构的高度为3μm,纳米级孔洞的大小约为100纳米,接触角大小为156°,反射率低于6%。According to the method and steps of Example 11, the electroless deposition of silver nanoparticles is changed to chemical vapor deposition, and the thickness of the deposited silver nanoparticles is 5nm. Other steps are the same as in Example 11, and a superhydrophobic anti-reflective silicon surface can also be obtained. The height of the silicon grid structure of the prepared structure is 3 μm, the size of the nanoscale hole is about 100 nanometers, the size of the contact angle is 156°, and the reflectivity is lower than 6%.
实施例15:Example 15:
按实施例11的方法与步骤,将无电沉积银纳米粒子改为化学气相沉积金纳米粒子,沉积金纳米粒子的厚度为5nm,其他步骤同实施例11,同样可以得到超疏水抗反射硅表面。制备结构的硅网格结构的高度为3μm,纳米级孔洞的大小约为100纳米,接触角大小为155°,反射率低于7%。According to the method and steps of Example 11, the electroless deposition of silver nanoparticles is changed to chemical vapor deposition of gold nanoparticles, and the thickness of the deposited gold nanoparticles is 5nm. The other steps are the same as in Example 11, and the superhydrophobic antireflection silicon surface can also be obtained. . The height of the silicon grid structure of the prepared structure is 3 μm, the size of the nanoscale holes is about 100 nanometers, the size of the contact angle is 155°, and the reflectivity is lower than 7%.
实施例16:Example 16:
(1)选取n~100型硅片,并对其表面进行清洁处理。处理的过程为:将硅片分别在丙酮、氯仿、乙醇、水中进行超声清洗,超声功率为100W,时间5min。然后将硅片放入到1%的HF溶液中5min,除去表面的二氧化硅,最后用去离子水清洗,高纯氮气吹干。(1) Select n-100 type silicon wafers, and clean the surface. The treatment process is as follows: ultrasonically clean the silicon wafer in acetone, chloroform, ethanol, and water respectively, with an ultrasonic power of 100W for 5 minutes. Then put the silicon chip into 1% HF solution for 5 minutes to remove the silicon dioxide on the surface, and finally wash it with deionized water and dry it with high-purity nitrogen gas.
(2)取少量热塑型高分子聚合物MRI~7030(Micro Resist公司,德国)或聚甲基丙烯酸甲酯PMMA旋涂于处理好的硅片表面上,旋涂厚度约为200~500nm,利用瑞典的OBDUCAT公司生产的2.5英寸纳米压印机,以氮化硅材料的模板(通过电子束刻蚀的方法构筑,点阵型结构,其点的大小尺寸范围为800nm×800nm~10μm×10μm,点的间距尺寸范围为800nm~10μm)构筑出高分子与模板结构互补的有序结构,即利用纳米压印的方法在基底表面构筑微米级结构。然后利用氧等离子体去掉点阵间聚合物阻挡层,露出硅片表面,然后将得到的样品通过RIE刻蚀来制备硅岛微结构,刻蚀的气体为SF6(30sccm)和CHF3(6sccm)(SF6:CHF3=5:1),刻蚀的功率100W,腔体压力30mTorr,刻蚀时间1000s。(2) Spin-coat a small amount of thermoplastic polymer MRI-7030 (Micro Resist, Germany) or polymethyl methacrylate PMMA on the surface of the treated silicon wafer with a spin-coating thickness of about 200-500 nm. Using a 2.5-inch nano-imprinting machine produced by Sweden's OBDUCAT company, a template of silicon nitride material (constructed by electron beam etching, a lattice structure, the size of the dots ranges from 800nm×800nm to 10μm×10μm, The pitch of the dots ranges from 800nm to 10μm) to construct an ordered structure that complements the polymer and the template structure, that is, to construct a micron-scale structure on the surface of the substrate by using the nanoimprint method. Then use oxygen plasma to remove the inter-lattice polymer barrier layer to expose the surface of the silicon wafer, and then the obtained sample is etched by RIE to prepare the silicon island microstructure. The etching gas is SF 6 (30 sccm) and CHF 3 (6 sccm ) (SF 6 :CHF 3 =5:1), the etching power is 100W, the cavity pressure is 30mTorr, and the etching time is 1000s.
(3)在微米级的硅岛表面制备纳米级孔洞,首先将表面制备了硅岛的硅片放入到HF/AgNO3(4.6和0.01M)溶液中,无电沉积银纳米粒子1分钟,然后,将表面长有银纳米粒子的硅岛结构放入到HF/H2O2/H2O溶液中(49%HF,30%H2O2和H2O的体积比为1:5:10),进行催化刻蚀30s,以制备纳米级孔洞。最后用硝酸将银纳米粒子洗去。(3) Prepare nanoscale pores on the surface of micron-scale silicon islands. First, put the silicon wafers with silicon islands on the surface into HF/AgNO 3 (4.6 and 0.01M) solution, and electrolessly deposit silver nanoparticles for 1 minute. Then, put the silicon island structure with silver nanoparticles on the surface into the HF/H 2 O 2 /H 2 O solution (the volume ratio of 49% HF, 30% H 2 O 2 and H 2 O is 1:5 : 10), performing catalytic etching for 30s to prepare nanoscale holes. Finally, the silver nanoparticles were washed away with nitric acid.
(4)对已制备的结构进行表面化学修饰,将得到的微米纳米复合结构放入干净的玻璃培养皿中,在培养皿底部滴0.5ml的十七氟癸基三甲氧基硅烷,加热到250℃,保持2.5h,然后冷却到室温。制备结构的硅岛高度为2.3μm,纳米级孔洞的大小约为100纳米,接触角大小为155°,反射率低于6%。(4) Carry out surface chemical modification to the prepared structure, put the obtained micro-nano composite structure into a clean glass petri dish, drop 0.5ml of heptadecafluorodecyltrimethoxysilane at the bottom of the petri dish, heat to 250 ℃, keep 2.5h, then cool to room temperature. The height of the silicon island of the prepared structure is 2.3 μm, the size of the nanoscale hole is about 100 nanometers, the size of the contact angle is 155°, and the reflectivity is lower than 6%.
实施例17:Example 17:
按实施例16的方法与步骤,将无电沉积银纳米粒子改为电沉积,电解液为0.01M的AgNO3溶液,沉积电压为400mv,沉积时间为15min,其他步骤同实施例11,同样可以得到超疏水抗反射硅表面。制备结构的硅岛高度为2.3μm,纳米级孔洞的大小约为130纳米,接触角大小为152°,反射率低于8%。According to the method and steps of Example 16, the electroless deposition of silver nanoparticles is changed to electrodeposition, the electrolyte is 0.01M AgNO solution, the deposition voltage is 400mv, and the deposition time is 15min. Other steps are the same as in Example 11, and can be A superhydrophobic antireflective silicon surface is obtained. The silicon island height of the prepared structure is 2.3 μm, the size of the nanoscale hole is about 130 nm, the contact angle is 152°, and the reflectivity is lower than 8%.
实施例18:Example 18:
按实施例16的方法与步骤,将无电沉积银纳米粒子改为电沉积金纳米粒子,电解液为0.01M的氯金酸溶液,沉积电压为500mv,沉积时间为10min,其他步骤同实施例11,同样可以得到超疏水抗反射硅表面。制备结构的硅岛高度为2.3μm,纳米级孔洞的大小约为120纳米,接触角大小为150°,反射率低于7%。According to the method and steps of Example 16, the electroless deposition of silver nanoparticles is changed to electrodeposition of gold nanoparticles, the electrolyte is 0.01M chloroauric acid solution, the deposition voltage is 500mv, and the deposition time is 10min. Other steps are the same as in the embodiment. 11. The superhydrophobic anti-reflection silicon surface can also be obtained. The height of the silicon island of the prepared structure is 2.3 μm, the size of the nanoscale hole is about 120 nm, the size of the contact angle is 150°, and the reflectivity is lower than 7%.
实施例19:Example 19:
按实施例16的方法与步骤,将无电沉积银纳米粒子改为化学气相沉积,沉积银纳米粒子的厚度为5nm,其他步骤同实施例11,同样可以得到超疏水抗反射硅表面。制备结构的硅岛高度为2.3μm,纳米级孔洞的大小约为100纳米,接触角大小为154°,反射率低于6%。According to the method and steps of Example 16, the electroless deposition of silver nanoparticles is changed to chemical vapor deposition, and the thickness of the deposited silver nanoparticles is 5nm. Other steps are the same as in Example 11, and a superhydrophobic antireflective silicon surface can also be obtained. The height of the silicon island of the prepared structure is 2.3 μm, the size of the nanoscale hole is about 100 nanometers, the size of the contact angle is 154°, and the reflectivity is lower than 6%.
实施例20:Example 20:
按实施例16方法与步骤,将无电沉积银纳米粒子改为化学气相沉积金纳米粒子,沉积金纳米粒子的厚度为5nm,其他步骤同实施例11,同样可以得到超疏水抗反射硅表面。制备结构的硅岛高度为2.3μm,纳米级孔洞的大小约为100纳米,接触角大小为155°,反射率低于7%。According to the method and steps of Example 16, the electroless deposition of silver nanoparticles is changed to chemical vapor deposition of gold nanoparticles, and the thickness of the deposited gold nanoparticles is 5nm. The height of the silicon island of the prepared structure is 2.3 μm, the size of the nanoscale hole is about 100 nanometers, the size of the contact angle is 155°, and the reflectivity is lower than 7%.
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