Self-assembled titanium calcium oxide nanopatterns as versatile reactive nanomasks for dry etching lithographic transfer with high selectivity

We report the simple preparation of ultra-thin self-assembled nanoperforated titanium calcium oxide films and their use as reactive nanomasks for selective dry etching of silicon. This novel reactive nanomask is composed of TiO2 in which up to 50% of Ti was replaced by Ca (CaxTi(1-x)O(2-x)). The system was prepared by evaporation induced self-assembly of dip-coated solution of CaCl2, TiCl4 and poly(butadiene-block-ethylene oxide) followed by 5 min of thermal treatment at 500 degrees C in air. The mask exhibits enhanced selectivity by forming a CaF2 protective layer in the presence of a chemically reactive fluorinated plasma. In particular it is demonstrated that ordered nano-arrays of dense Si pillars, or deep cylindrical wells, with high aspect ratio i.e. lateral dimensions as small as 20 nm and height up to 200 nm, can be formed. Both wells and pillars were formed by tuning the morphology and the homogeneity of the deposited mask. The mask preparation is extremely fast and simple, low-cost and easily scalable. Its combination with reactive ion etching constitutes one of the first examples of what can be achieved when sol-gel chemistry is coupled with top-down technologies. The resulting Si nanopatterns and nanostructures are of high interest for applications in many fields of nanotechnology including electronics and optics. This work extends and diversifies the toolbox of nanofabrication methods.