Direction-Dependent Properties in Inverted Carbon Nitride Colloidal Glasses with Gradient Porosity

It is well known that the step from a dense packing of colloidal beads to the inverted systems was important for the optimization of photonic crystal properties. Inverted opals made of high-refractive index semiconductors have attracted great attention due to their supreme optical features such as the occurrence of a photonic band-gap and because of an astonishing behavior in photocatalysis or for photovoltaics caused by so-called slow photons. It is much less known that photonic glasses, despite being disordered, exhibit unique optical properties too like random lasing or high-contrast structural colors. In analogy to opals and inverted opals, one can expect that inverted colloidal glasses may lead to an amplification of photonic properties as well or even to the emergence of unexpected features. An inverted photonic glass is characterized by a dense packing of monodisperse voids with colloidal dimensions without any long-range order. The preparation of inverse photonic glasses has rarely been reported by now and cases for materials composed of a semiconductor as a pore-wall material are unknown. The synthesis of porous carbon nitride (C₃N₄) with inverted colloidal glass structure is demonstrated here using a template approach. The formation of the template with glass-like order is achieved by analytical ultracentrifugation (AUZ) of size-selected silica colloids, followed by infiltration of a precursor sol, transformation to carbon nitride and the final removal of the template. The use of AUZ is particularly important because it even allows to use a mixture of differently sized template particles, which are gradually fractionated. Monoliths with optimized morphological features exhibiting a gradient porosity and highly accessible pores are obtained. The result are materials with a graded structure. What makes such functional gradient material interesting is, a dependence of the optical features on the position can be expected. In addition, the method presented here allows to synthesize materials with adjustable composition ranging from carbon over nitrogen-doped carbon to C₃N₄ with either graphitic or polymeric structure. Therefore, the optical band gap is highly adjustable and tunable with regards to the photonic properties, as confirmed by optical absorption and photoluminescence measurements.