coatings on geometrically complex substrates, [2][3][4] such as anodic aluminum oxide membranes, aerogels, photonic crystals, and nanorods, with a film thickness control on the Å-scale. Additionally, by combining two or more binary ALD processes in a super cycle ALD process, multicomponent materials can be achieved, such as nanolaminates, doped thin films, and ternary or quaternary oxides. [5] The ability of compositional control of thin films at an atomic level provides the possibility for development of tailor-made atomically mixed systems, pointing to novel materials functionalities.Direct and inverse opals are examples of photonic crystals, which can be manufactured by colloidal self-assembly [6,7] and ALD. [8,9] Its high ordered porosity of interconnects is attractive for a variety of technological applications, such as porous membranes, catalysts, solid oxide fuel cells, and photonics applications. [10][11][12] The 3D periodic arrangement of pores provides a photonic bandgap to these artificial materials, which prohibits the transmission and hence leads to a reflection of electromagnetic radiation in spectral range which is determined by the materials' properties. Specifically, the radiation wavelength, which will be reflected, is influenced by the material microstructure assemble, mono-or multistacked, and also the macropore size. [8,9,[13][14][15] This selective behavior in transmission and reflection might pave the way to effective solar thermo photovoltaic energy conversion devices [16,17] and also next-generation thermal barrier coatings.However, retention of the 3D structure for high-temperature applications remains a significant challenge. [10,18] As the length scales in these porous materials are decreased, as higher is the surface area and specific activity. When exposed to high temperatures, the material's structure may suffer from detrimental morphological changes, such as extensive grain growth, distortion, and eventually destruction of the total periodically organized structure. [9,10] Therefore, this material needs to not only interact with electromagnetic radiation but also have structural stability and keep its function up to high temperatures (usually higher than 1000 °C). The latter fact could be addressed by coating the substrate material with a ceramic oxide that is stable at high temperatures, either by chemical vapor deposition (CVD) [19] or ALD [20] processes.Herein, mullite has been chosen: A ceramic material, which is well known for its stability at high-temperature environments, Atomic layer deposition (ALD) process presents thickness control in an Ång-strom scale due to its inherent surface self-limited reactions. In this work, an ALD super cycle approach, where a superposition of nanolaminates of SiO 2 and Al 2 O 3 is generated by cycling the precursors APTES-H 2 O-O 3 and TMA-H 2 O, is used to deposit thin films with varying ratio of Al 2 O 3 :SiO 2 into silicon wafers and into inverse photonic crystals. The resulting ternary oxide films deposited at low temperature (150 °C) ar...