Power dissipation is a crucial problem as the packing density of transistors increases in modern integrated circuits. Tunnel field-effect transistors (TFETs), which have high energy filtering provided by band-to-band tunneling (BTBT), have been proposed as an alternative electronics architecture to decrease the energy loss in bias operation and to achieve steep switching at room temperature. Very recently, the BTBT behavior has been demonstrated in van der Waals heterostructures by using unintentionally doped semiconductors. The reason of the BTBT formation is attributed to a significant band bending near the heterointerface, resulting in carrier accumulations. In this work, to investigate charge transport in type-III transistors, we adopted the same band-bending concept to fabricate van der Waals BP/MoS2 heterostructures. Through analyzing the temperature dependence of their electrical properties, we carefully ruled out the contribution of metal-semiconductor contact resistances and improved our understanding of carrier injection in 2D type-III transistors. The BP/MoS2 heterostructures showed both negative differential resistance and 1/f 2 current fluctuations, strongly demonstrating the BTBT operation. Finally, we also designed a TFET based on this heterostructure with an ionic liquid gate, and this TFET demonstrated an subthreshold slope can successfully surmount the thermal limit of 60 mV/decade. This work improves our understanding of charge transport in such layered heterostructures and helps to improve the energy efficiency of next-generation nanoscale electronics.