Fundamental Efficiency Limits of Transition-Metal Dichalcogenide Solar Cells with Carrier Multiplication and Hot-Carrier Effects

Abstract

Detailed-balance limits for transition-metal dichalcogenide (TMD) solar cells have been reported, but existing TMD-specific limits do not simultaneously resolve thickness-dependent optics, carrier multiplication (CM), hot-carrier (HC) extraction, and finite cooling leakage. Here, we develop a generalized detailed-balance theory that provides an upper-bound framework. The model combines energy- and thickness-dependent absorptance a(E,d), exciton-resolved monolayer absorbance, an experimentally available CM quantum-yield limit (eta_CM <= 0.97), and an endoreversible HC engine with ideal energy-selective contacts and finite heat-leak coefficient kappa. The framework shows that CM and HC draw on the same above-gap photon-energy reservoir; therefore, CM does not raise the reversible HC thermodynamic limit. Instead, CM can protect finite-kappa performance only by shifting excess-energy utilization from a cooling-sensitive voltage channel into collected current. For optically thick TMDs under AM1.5G illumination, the SQ optimum lies near E_g = 1.3 eV, whereas the CM/HC-favored envelope shifts toward E_g = 1.0 eV with reversible efficiencies above 50%. For monolayer TMDs such as WSe2 (E_g = 1.63 eV), CM is essentially inactive because only about 3.7% of above-gap AM1.5G photons satisfy E > 2E_g, giving an idealized short-circuit-current gain of only about 0.6% before device nonidealities. Bulk-like TMDs can show large HC-related gains at d = 10-50 nm, but even kappa = 0.2 W m^-2 K^-1 implies about 100 W m^-2 heat leak for Delta T = 500 K. Thus, high-E_g monolayer TMDs are not promising one-sun CM candidates, whereas narrow-E_g, bulk-like TMD absorbers remain plausible beyond-SQ candidates only if energy-selective extraction and phonon-engineered cooling suppression are realized together.