Controllable Design of “Nested Doll” MoS₂/V₂O₃ Heterostructures Promotes Polarization Effects for High‐Efficiency Microwave Absorption

Abstract Special multilayer heterostructures and lattice modulation play a crucial role in the field of microwave absorption. Herein, a unique “nested doll” MoS 2 /V 2 O 3 heterostructures are synthesized via crystal epitaxy growth and solvothermal strategy. The synchronized modulation of lattice spacing and interfacial vacancies in MoS 2 nanosheets is achieved by adjusting the S 2 ⁻ concentration. A high concentration of S 2 ⁻ expands the MoS 2 lattice spacing and increases interfacial vacancies, facilitating the precise modulation of the orderly arrangement of MoS 2 ‐V 2 O 3 ‐MoS 2 layers and inducing interfacial polarization. By increasing the number of V 2 O 3 ‐MoS 2 layers from two to five, a built‐in electric field is formed, which enhances charge transfer from the MoS 2 surface to the V 2 O 3 core. The introduction of vacancies reduces the MoS 2 band gap, lowers the electron hopping barrier, increases dielectric loss, and ultimately synergistically improves microwave absorption (MA). As a result, the “nested doll” MoS 2 /V 2 O 3 ‐5 (5 layers) microspheres exhibit superior MA behavior compared to other MoS 2 /V 2 O 3 absorbers. The reflection loss reaches −69.65 dB and the effective absorption bandwidth achieves 7.68 GHz. These discoveries have contributed to the further development of multilayer heterostructures and improved advances in the theory of energy band structures and electromagnetic properties.