RESUMEN
The successful design and device integration of nanoscale heterointerfaces hinges upon precise manipulation of both ground- and excited-state charge carrier (electron and hole) densities. However, it is particularly challenging to quantify these charge carrier densities in nanoscale materials, leading to uncertainties in the mechanisms of many carrier density-dependent properties and processes. Here, we demonstrate a method that utilizes steady-state and transient absorption spectroscopies to correlate monolayer MoS2 electron density with the easily measured metric of excitonic optical absorption quenching in a variety of mixed-dimensionality s-SWCNT/MoS2 heterostructures. By employing a 2D phase-space filling model, the resulting correlation elucidates the relationship between charge density, local dielectric environment, and concomitant excitonic properties. The phase-space filling model is also able to describe existing trends from the literature on transistor-based measurements on MoS2, WS2, and MoSe2 monolayers that were not previously compared to a physical model, providing additional support for our method and results. The findings provide a pathway to the community for estimating both ground- and excited-state carrier densities in a wide range of TMDC-based systems.
RESUMEN
Innovation in optoelectronic semiconductor devices is driven by a fundamental understanding of how to move charges and/or excitons (electron-hole pairs) in specified directions for doing useful work, e.g., for making fuels or electricity. The diverse and tunable electronic and optical properties of two-dimensional (2D) transition metal dichalcogenides (TMDCs) and one-dimensional (1D) semiconducting single-walled carbon nanotubes (s-SWCNTs) make them good quantum confined model systems for fundamental studies of charge and exciton transfer across heterointerfaces. Here we demonstrate a mixed-dimensionality 2D/1D/2D MoS2/SWCNT/WSe2 heterotrilayer that enables ultrafast photoinduced exciton dissociation, followed by charge diffusion and slow recombination. Importantly, the heterotrilayer serves to double charge carrier yield relative to a MoS2/SWCNT heterobilayer and also demonstrates the ability of the separated charges to overcome interlayer exciton binding energies to diffuse from one TMDC/SWCNT interface to the other 2D/1D interface, resulting in Coulombically unbound charges. Interestingly, the heterotrilayer also appears to enable efficient hole transfer from SWCNTs to WSe2, which is not observed in the identically prepared WSe2/SWCNT heterobilayer, suggesting that increasing the complexity of nanoscale trilayers may modify dynamic pathways. Our work suggests "mixed-dimensionality" TMDC/SWCNT based heterotrilayers as both interesting model systems for mechanistic studies of carrier dynamics at nanoscale heterointerfaces and for potential applications in advanced optoelectronic systems.
RESUMEN
High-performance semiconductor materials and devices are needed to supply the growing energy and computing demand. Organic semiconductors (OSCs) are attractive options for opto-electronic devices, due to their low cost, extensive tunability, easy fabrication, and flexibility. Semiconducting single-walled carbon nanotubes (s-SWCNTs) have been extensively studied due to their high carrier mobility, stability and opto-electronic tunability. Although molecular charge transfer doping affords widely tunable carrier density and conductivity in s-SWCNTs (and OSCs in general), a pervasive challenge for such systems is reliable measurement of charge carrier density and mobility. In this work we demonstrate a direct quantification of charge carrier density, and by extension carrier mobility, in chemically doped s-SWCNTs by a nuclear magnetic resonance approach. The experimental results are verified by a phase-space filling doping model, and we suggest this approach should be broadly applicable for OSCs. Our results show that hole mobility in doped s-SWCNT networks increases with increasing charge carrier density, a finding that is contrary to that expected for mobility limited by ionized impurity scattering. We discuss the implications of this important finding for additional tunability and applicability of s-SWCNT and OSC devices.
