Carrier multiplication (CM) is a process in which high-energy free carriers relax by generation of additional electron-hole pairs rather than by heat dissipation. CM is promising disruptive improvements in photovoltaic energy conversion and light detection technologies. Current state-of-the-art nanomaterials including quantum dots and carbon nanotubes have demonstrated CM, but are not satisfactory owing to high-energy-loss and inherent difficulties with carrier extraction. Here, we report CM in van der Waals (vdW) MoTe₂ and WSe₂ films, and find characteristics, commencing close to the energy conservation limit and reaching up to 99% CM conversion efficiency with the standard model. This is demonstrated by ultrafast optical spectroscopy with independent approaches, photo-induced absorption, photo-induced bleach, and carrier population dynamics. Combined with a high lateral conductivity and an optimal bandgap below 1 eV, these superior CM characteristics identify vdW materials as an attractive candidate material for highly efficient and mechanically flexible solar cells in the future.

Although large exciton binding energies of typically 0.6–1.0 eV are observed for monolayer transition metal dichalcogenides (TMDs) owing to strong Coulomb interaction, multilayered TMDs yield relatively low exciton binding energies owing to increased dielectric screening. Recently, the ideal carrier-multiplication threshold energy of twice the bandgap has been realized in multilayered semiconducting 2H-MoTe₂ with a conversion efficiency of 99%, which suggests strong Coulomb interaction. However, the origin of strong Coulomb interaction in multilayered 2H-MoTe₂, including the exciton binding energy, has not been elucidated to date. In this study, unusually large exciton binding energy is observed through optical spectroscopy conducted on CVD-grown 2H-MoTe₂. To extract exciton binding energy, the optical conductivity is fitted using the Lorentz model to describe the exciton peaks and the Tauc–Lorentz model to describe the indirect and direct bandgaps. The exciton binding energy of 4 nm thick multilayered 2H-MoTe₂ is approximately 300 meV, which is unusually large by one order of magnitude when compared with other multilayered TMD semiconductors such as 2H-MoS₂ or 2H-MoSe₂. This finding is interpreted in terms of small exciton radius based on the 2D Rydberg model. The exciton radius of multilayered 2H-MoTe₂ resembles that of monolayer 2H-MoTe₂, whereas those of multilayered 2H-MoS₂ and 2H-MoSe₂ are large when compared with monolayer 2H-MoS₂ and 2H-MoSe₂. From the large exciton binding energy in multilayered 2H-MoTe₂, it is expected to realize the future applications such as room-temperature and high-temperature polariton lasing.

Transition metal dichalcogenide (TMD) layered semiconductors possess immense potential in the design of photonic, electronic, optoelectronic, and sensor devices. However, the sub-bandgap light absorption of TMD in the range from near-infrared (NIR) to short-wavelength infrared (SWIR) is insufficient for applications beyond the bandgap limit. Herein, we report that the sub-bandgap photoresponse of MoS₂/Au heterostructures can be robustly modulated by the electrode fabrication method employed. We observed up to 60% sub-bandgap absorption in the MoS₂/Au heterostructure, which includes the hybridized interface, where the Au layer was applied via sputter deposition. The greatly enhanced absorption of sub-bandgap light is due to the planar cavity formed by MoS₂ and Au; as such, the absorption spectrum can be tuned by altering the thickness of the MoS₂ layer. Photocurrent in the SWIR wavelength range increases due to increased absorption, which means that broad wavelength detection from visible toward SWIR is possible. We also achieved rapid photoresponse (~150 µs) and high responsivity (17 mA W⁻¹) at an excitation wavelength of 1550 nm. Our findings demonstrate a facile method for optical property modulation using metal electrode engineering and for realizing SWIR photodetection in wide-bandgap 2D materials.