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Abstract Germanium sulfide (GeS) is a 2D semiconductor with potential for high-speed optoelectronics and photovoltaics due to its near-infrared band gap and high mobility of optically excited charge carriers. Here, we use time-resolved THz spectroscopy to investigate the differences in ultrafast carrier dynamics in GeS following near-band gap photoexcitation (1.55 eV), which penetrates deep into the multilayer GeS, and excitation with above-band gap photon energy (3.1 eV), which is absorbed within a sub-20 nm surface layer. We find that the photoexcited carriers in the bulk have significantly longer lifetimes and higher mobility, as they are less impacted by trap states that affect carrier behavior in the surface layer. These insights are important for designing GeS-based photodetectors, solar energy conversion devices, and sensors that leverage the sensitivity of surface-layer photoexcited carriers to trap states. 

SnS2 is a two-dimensional (2D) layered semiconductor with a visible-range bandgap (~2.3eV), high charge carrier mobility, long carrier lifetimes, and good environmental stability. This study explores the impact of zero-valent metal intercalation into the van der Waals gaps of SnS2 on charge carrier dynamics. We demonstrate that metal intercalation enhances optical absorption in the yellow-to-IR range and induces metal-dependent bandgap shifts. Time-resolved THz spectroscopy reveals that different metals uniquely influence photoconductivity dynamics: We find that intercalation with Bi, Ni, and Fe shortens the photoconductivity decay times, whereas Rh intercalation results in a slower decay. These findings highlight the potential of metal intercalation to tailor SnS2 properties for diverse applications, from solar energy conversion to high-speed photodetectors. 

We report on THz emission in single-crystalline SnS2 in response to above bandgap excitation. Symmetry properties of THz generation suggest that its origin is an ultrafast surface shift current, a 2nd order nonlinear effect that can occur as a result of above-gap photoexcitation of a non-centrosymmetric semiconductor. Multilayer SnS2 can exist in several polytypes that differ in the layer stacking. Of those polytypes, 2H and 18R are centrosymmetric while 4H is not. While Raman spectroscopy suggests that the single crystalline SnS2 in our experiments is 2H, its THz emission has symmetry that are fully consistent with the P3m1 phase of 4H polytype. We hypothesize that the stacking disorder, where strain-free stacking faults that interrupt regions of 2H polytype, can break inversion symmetry and result in THz emission. These results lay the foundations for application of SnS2 as an efficient, stable, flexible THz source material, and highlight the use of THz spectroscopy as a sensitive tool for establishing symmetry properties of materials. 

Two-dimensional, 2D, niobium carbide MXene, Nb2CTx, has attracted attention due to its extraordinarily high photothermal conversion efficiency that has applications ranging from medicine, for tumor ablation, to solar energy conversion. Here, we characterize its electronic properties and investigate the ultrafast dynamics of its photoexcitations with a goal of shedding light onto the origins of its unique properties. Through density functional theory, DFT, calculations, we find that Nb2CTx is metallic, with a small but finite DOS at the Fermi level for all experimentally relevant terminations that can be achieved using HF or molten salt etching of the parent MAX phase, including –OH, –O, –F, –Cl, –Br, –I. In agreement with this prediction, THz spectroscopy reveals an intrinsic long-range conductivity of ∼60 Ω−1 cm−1, with significant charge carrier localization and a charge carrier density (∼1020 cm−3) comparable to Mo-based MXenes. Excitation with 800 nm pulses results in a rapid enhancement in photoconductivity, which decays to less than 25% of its peak value within several picoseconds, underlying efficient photothermal conversion. At the same time, a small fraction of photoinjected excess carriers persists for hundreds of picoseconds and can potentially be utilized in photocatalysis or other energy conversion applications. 

GeS and GeSe are 2D semiconductors with band gaps in the near infrared and predicted high carrier mobility. We find that excitation with 800 nm pulses results in long-lived free photocarriers, persisting for hundreds of picoseconds, in GeS and GeSe noribbons. We also demonstrate that zerovalent Cu intercalation is an effective tool for tuning the photoconductive response. Intercalation of ~ 3 atomic % of zerovalent Cu reduces the carrier lifetime in GeSe and GeS. In GeS, it also shortens the photoconductivity rise and improves carrier mobility. 

Germanium sulfide (GeS) and germanium selenide (GeSe) are layered 2D van der Waals materials that belong to a family of group-IV monochalcogenides. These semiconductors have high carrier mobilities and moderate band gaps in the near infrared. Additionally, we have demonstrated that above gap photoexcitation results in ultrafast surface photocurrents and emission of THz pulses due to a spontaneous ferroelectric polarization that breaks inversion symmetry in the monolayer. Beyond the sub-picosecond time scales of shift currents, photoexcited carriers in both materials result in long-lived transient conductivity. We find that 800 nm excitation results in longer lived free photocarriers, persisting for hundreds of picoseconds to several nanoseconds, compared to tens to hundreds of picoseconds lifetimes for 400 nm excitation. Here, we report on tailoring the free photoexcited carrier lifetimes by intercalation of zero-valent Cu into the van der Waals gaps of GeS and GeSe. Density functional theory calculations predict that Cu atoms introduce mid-gap states. We demonstrate that intercalating only ∼3 atomic % of zero-valent Cu reduces the carrier lifetime by as much as two-to-four-fold, raising the prospects of these materials being used for high-speed optoelectronics.