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We also introduce an efficient technique by tuning the vacancy defects on the solid surface to tune the atomic structure as well as the thermal transfer. Our study reveals the complex relationship between the atomic structure of the crystal face, the water layer structure and the thermal boundary conductance, which will inspire more experimental and theoretical studies toward the improvement of interfacial thermal transport by tuning the structure of the water layer.A phase transition material, VO2, with a semiconductor-to-metal transit