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Facile Fabrication of Multifunctional ZnO Urchins on Surfaces

机译：在表面上方便地制备多功能ZnO顽童

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Functional ZnO nanostructured surfaces are important in a wide range of applications. Here we report the simple fabrication of ZnO surface structures at near room temperature with morphology resembling that of sea urchins, with densely packed, μ m-long, tapered nanoneedles radiating from the urchin center. The ZnO urchin structures were successfully formed on several different substrates with high surface density and coverage, including silicon (Si), glass, polydimethylsiloxane (PDMS), and copper (Cu) sheets, as well as Si seeded with ZnO nanocrystals. Time-resolved SEM revealed growth kinetics of the ZnO nanostructures on Si, capturing the emergence of “infant” urchins at the early growth stage and subsequent progressive increases in the urchin nanoneedle length and density, whilst the spiky nanoneedle morphology was retained throughout the growth. ε -Zn(OH)2 orthorhombic crystals were also observed alongside the urchins. The crystal structures of the nanostructures at different growth times were confirmed by synchrotron X-ray diffraction measurements. On seeded Si substrates, a two-stage growth mechanism was identified, with a primary growth step of vertically aligned ZnO nanoneedle arrays preceding the secondary growth of the urchins atop the nanoneedle array. The antibacterial, anti-reflective, and wetting functionality of the ZnO urchins—with spiky nanoneedles and at high surface density—on Si substrates was demonstrated. First, bacteria colonization was found to be suppressed on the surface after 24 h incubation in gram-negative Escherichia coli (E. coli) culture, in contrast to control substrates (bare Si and Si sputtered with a 20 nm ZnO thin film). Secondly, the ZnO urchin surface, exhibiting superhydrophilic property with a water contact angle ~ 0 ° , could be rendered superhydrophobic with a simple silanization step, characterized by an apparent water contact angle θ of 159° ± 1.4° and contact angle hysteresis Δ θ & 7°. The dynamic superhydrophobicity of the surface was demonstrated by the bouncing-off of a falling 10 μ L water droplet, with a contact time of 15.3 milliseconds (ms), captured using a high-speed camera. Thirdly, it was shown that the presence of dense spiky ZnO nanoneedles and urchins on the seeded Si substrate exhibited a reflectance R & 1% over the wavelength range λ = 200–800 nm. The ZnO urchins with a unique morphology fabricated via a simple route at room temperature, and readily implementable on different substrates, may be further exploited for multifunctional surfaces and product formulations.
机译：功能性ZnO纳米结构表面在广泛的应用中很重要。在这里，我们报道了在接近室温的情况下，ZnO表面结构的简单制造，其形态类似于海胆，密集堆积，μ。从海胆中心放射出m米长的锥形纳米针。 ZnO顽童结构成功地在几种具有高表面密度和覆盖率的不同基底上形成，包括硅（Si），玻璃，聚二甲基硅氧烷（PDMS）和铜（Cu）片以及掺有ZnO纳米晶体的Si。时间分辨的SEM揭示了ZnO纳米结构在Si上的生长动力学，捕获了“婴儿”的出现。处于生长早期的海胆以及随后的海胆纳米针长度和密度逐渐增加，而尖刺的纳米针形态则在整个生长过程中得以保留。 ＆epsilon;在海胆旁边还观察到-Zn（OH）2正交晶体。通过同步加速器X射线衍射测量证实了在不同生长时间的纳米结构的晶体结构。在晶种的Si衬底上，确定了一个两阶段的生长机制，即在纳米针阵列顶部的海胆的第二次生长之前，垂直排列的ZnO纳米针阵列的主要生长步骤。展示了具有尖锐的纳米针且高表面密度的ZnO顽童的抗菌，抗反射和润湿功能-在Si基板上。首先，发现与革兰氏阴性大肠杆菌（E. coli）培养物相比，与对照基质（裸Si和用20 nm ZnO薄膜溅射的Si）相比，细菌定殖在革兰氏阴性大肠杆菌（E. coli）培养物中孵育24小时后，其表面被抑制。其次，ZnO野孩子表面表现出超亲水性，水接触角约为0°。可以通过简单的硅烷化步骤使其具有超疏水性，其特征在于明显的水接触角θ。 159＆deg; ＆plusmn; 1.4度和接触角磁滞＆Delta; ＆theta; ＆ 7°。表面的动态超疏水性通过下降10μm的反弹来证明。使用高速相机拍摄的L水滴，接触时间为15.3毫秒（ms）。第三，表明在晶种的Si衬底上存在致密的尖刺的ZnO纳米针和野孩子的反射率R ＜3。在波长范围λ上为1％; = 200-800 nm。可以通过在室温下通过简单的途径制造的，且易于在不同基材上实施的具有独特形态的ZnO顽童，可进一步用于多功能表面和产品配方。

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