Epsilon-negative materials (ENMs) has become a research hotspot due to their unique physical properties and practical applications in fields such as directional radiation and tunneling effects. In this work, weakly negative permittivity (from -50 at 10 kHz to -25 at 1 MHz) was realized from three-dimensional printed polydimethylsiloxane/graphene films. The dielectric properties including complex permittivity (ε', ε″), complex impedance (Z', Z″), alternating current conductivity (σac), and dielectric loss tangent (tanδ) were investigated. When graphene content reached 15 wt%, the interconnected graphene network was formed, resulting in negative permittivity. Theory calculations were further used to explore the mechanism. The electrons around carbon atoms showed significant delocalization. With the effect of the external electromagnetic field, the electrons on the surface of graphene could easily oscillate collectively, leading to negative permittivity. Differential charge density exhibited that interfacial electric fields were formed between polydimethylsiloxane and graphene, enhancing positive permittivity. Therefore, when the graphene content reached 15 wt%, the film exhibited weakly negative permittivity, which was the result of the mutual balance between the graphene conductive network and the interface electric fields.
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