  In designing material functionality within the intricate realm of transition
metal oxides, lattice structure and d-orbital occupancy are two principal
determinants of the correlated physical properties, such as superconductivity.
However, the modulation of these two factors is inherently limited by the need
to balance thermodynamic stability, kinetic mobility, and synthesis precision,
particularly for oxidation-demanding phases. We introduce a methodology, namely
the gigantic-oxidative atomically layered epitaxy (GOAL-Epitaxy), enhancing
oxidation power 3-4 orders of magnitude beyond oxide molecular beam epitaxy
(OMBE) and pulsed laser deposition (PLD), while ensuring atomic-layer-by-layer
growth of designed complex structures. Consequently, thermodynamic stability is
markedly augmented at elevated temperatures, improving growth kinetics. We
demonstrate the accurate synthesis of complex nickelates and cuprates,
especially an artificially designed structure as a parent of high-temperature
superconductivity, in which alternating single and double NiO2 layers possess
distinct nominal d-orbital occupancy. The GOAL-Epitaxy enables material
discovery within the vastly broadened growth parameter space.
