A novel ZnO dry etching approach is introduced using reactive ion beam etching of thick sol-gel ZnO layers for controlled nanodisk/nanocone array fabrication. In this approach the same system can be used for the colloidal lithography mask (silica particles) size reduction by a fluorine-based chemistry and etching of the ZnO nanostructures by a CH 4 /H 2 /Ar chemistry. This resulted in a ZnO:SiO 2 etch selectivity of ∼3.4 and etch rate of ∼56 nm/min. Thick sol-gel ZnO layers, nanodisk arrays and (truncated) nanocone arrays were fabricated and their optical properties analyzed by finite-difference time-domain simulations and spectrally-resolved total/specular reflectivity measurements. The demonstrated broadband omnidirectional anti-reflection, controlled nanostructure period/geometry and low absorption in the visible-NIR spectrum makes these sol-gel ZnO nanostructures very interesting for many optoelectronic applications, including photovoltaics. ZnO is a wide bandgap (∼3.37 eV at room temperature) II-VI semiconductor. Predominantly it crystalizes in the Wurtzite crystal structure and bulk ZnO has a refractive index of n ≈ 1.9-2.2 in the NIR-visible wavelength range. Some of the features of ZnO interesting for photovoltaic applications are its high transparency in the visible-NIR spectrum, a wide bandgap, a large exciton binding energy (60 meV at room temperature), non-centrosymmetric structure, strong room temperature luminescence and biocompatibility.
1,2ZnO has been studied extensively as a candidate for a number of applications, e.g., transparent conductive electrodes, optical waveguides, piezo-electric transducers, acoustic wave devices, conductive gas sensors, solar cell windows and biosensing. [1][2][3][4][5][6][7][8][9][10][11][12][13][14] Here, a sol-gel method has been developed and used for the fabrication of (relatively) thick porous polycrystalline ZnO layers. A similar method has already been reported for thin films by, e.g., Gohdsi et al. 34 and Choudhury et al. 44 Here the method has been extended for obtaining well-defined thick ZnO films (up to ∼2 μm) by using a sequential drop-cast approach in a 'vacuum' environment. The 'building' of these sequential ZnO layers to one thick layer provides a method to tune specific layer thicknesses on the micro/nanoscale. Other approaches for obtaining thick porous ZnO layers have been reported. [45][46][47] The sol-gel method is attractive since it is simple, cheap and straight forward. In addition, this method offers the flexibility to provide ZnO layers on a variety of surfaces. Sol-gel layers, consisting of crystals with c-axis orientation vertical to the surface, can be * Electrochemical Society Member.z E-mail: dvisser@kth.se obtained when the substrate material has a similar Wurtzite crystal structure to ZnO, e.g., GaN, SiC and (0001)-sapphire. For other types of substrates dense sol-gel layers, composed of non-specific direction, can still be obtained. In this work, thick ZnO layers have been fabricated and nanostructured on a Si substrate. These laye...