摘要： Layered nonstoichiometric vanadium oxides have aroused strong interest in energy conversion, storage, chemical catalysis, sensors and optoelectronic devices. It is still a critical challenge to control unique atomic-layer constructions and oxygen-dependent multivalent states in layered metal oxides. Here, we demonstrated the layered nonstoichiometric V7O16 thin films with controlled multivalent states and crystalline phases obtained by the combination of atomic layer deposition (ALD) and oxygen-dependent crystallization. The nonstoichiometric composition and crystalline microstructures are dominated by the oxidation states of vanadium and the thicknesses of the pristine films during the formation of layered V7O16 thin films. Variable-temperature optical and electrical behaviors suggest that no abrupt electronic and structural transitions are observed in the layered V7O16 thin films at a temperature ranging from 78 to 475 K. We expect that the oxygen-dependent multivalent states and crystalline phases in layered V7O16 will provide more opportunities to fabricate layered oxides and electrochemical devices based on nonstoichiometric vanadium oxides.