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

TL;DR

This paper develops a comprehensive detailed-balance model for TMD solar cells, analyzing the impacts of carrier multiplication and hot-carrier effects on efficiency limits considering thickness, optics, and heat leakage.

Contribution

It introduces a generalized framework combining optical, excitonic, and thermodynamic factors to evaluate TMD solar cell efficiency limits with carrier multiplication and hot-carrier effects.

Findings

Carrier multiplication does not increase the reversible hot-carrier limit.

Optimal bandgap for thick TMDs under AM1.5G is near 1.3 eV, shifting to 1.0 eV with high efficiencies.

Monolayer TMDs like WSe2 have limited carrier multiplication due to photon energy constraints.

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.