Dimensional Crossover Engineering in MoS 2 /Organic Superlattices Breaks the zT Barrier for 2D Thermoelectrics

Abstract The rapid development of self‐powered microelectronics demands thermoelectric devices (TEDs) that can simultaneously achieve high energy conversion efficiency and silicon micro‐fabrication compatibility. While for conventional bulk TEs, their incompatibility with silicon micro‐manufacturing restricts microelectronic integration. 2D materials, though CMOS‐fabrication‐friendly and widely explored for microelectronic devices, face critical limitations in thermoelectric energy conversion efficiency due to their low zT values (<0.2) stemming from unfavorable thermal conductivity‐power factor tradeoffs. These challenges are overcome through orbital‐property‐driven dimensional engineering of hybrid MoS 2 /organic superlattices, which synergistically enhances electrical transport while suppressing thermal conductivity. Strain‐adaptive intercalation of tert‐butylamine (TBA) molecules creates MoS 2 bilayer superlattices exhibiting an electronic structure crossover between monolayer‐like and bulk‐like characteristics, thereby maximizing the density of states near the Fermi level. The optimized MoS 2 bilayer/TBA hybrid superlattice achieves a breakthrough zT of 0.6 at 373 K – 12‐fold higher than monolayer counterparts and 100× surpassing bulk crystals. This represents the highest experimentally reported zT for 2D material‐based TEDs, approaching performance benchmarks of commercial bulk TEs. The work establishes a paradigm of dimensional engineering in hybrid superlattices, thus enabling integration of high‐efficiency 2D materials‐based TEDs into silicon microelectronics–a critical step toward self‐powered IoT systems and wearable technologies.