Multiphoton-pumped UV-Vis transient absorption spectroscopy of 2D materials: basic concepts and recent applications.

2D materials are considered a key element in the development of next-generation electronics (nanoelectronics) due to their extreme thickness in the nanometer range and unique physical properties. The ultrafast dynamics of photoexcited carriers in such materials are strongly influenced by their interfaces, since the thickness of 2D materials is much smaller than the typical depth of light penetration into their bulk counterparts and the mean free path of photoexcited carriers. The resulting collisions of photoexcited carriers with interfacial potential barriers of 2D materials in the presence of a strong laser field significantly alter the overall dynamics of photoexcitation, allowing laser light to be directly absorbed by carriers in the conduction/valence band through the inverse bremsstrahlung mechanism. The corresponding ultrafast carrier dynamics can be monitored using multiphoton-pumped UV-Vis transient absorption spectroscopy. In this review, we discuss the basic concepts and recent applications of this spectroscopy for a variety of 2D materials, including transition-metal dichalcogenide monolayers, topological insulators, and other 2D semiconductor structures.

Ultrafast Dynamics of Valley-Polarized Excitons in WSe2 Monolayer Studied by Few-Cycle Laser Pulses.

We report on the experimental investigation of the ultrafast dynamics of valley-polarized excitons in monolayer WSe2 using transient reflection spectroscopy with few-cycle laser pulses with 7 fs duration. We observe that at room temperature, the anisotropic valley population of excitons decays on two different timescales. The shorter decay time of approximately 120 fs is related to the initial hot exciton relaxation related to the fast direct recombination of excitons from the radiative zone, while the slower picosecond dynamics corresponds to valley depolarization induced by Coloumb exchange-driven transitions of excitons between two inequivalent valleys.

Photoluminescence Enhancement by Band Alignment Engineering in MoS2/FePS3 van der Waals Heterostructures.

Single-layer semiconducting transition metal dichalcogenides (2H-TMDs) display robust excitonic photoluminescence emission, which can be improved by controlled changes to the environment and the chemical potential of the material. However, a drastic emission quench has been generally observed when TMDs are stacked in van der Waals heterostructures, which often favor the nonradiative recombination of photocarriers. Herein, we achieve an enhancement of the photoluminescence of single-layer MoS2 on top of van der Waals FePS3. The optimal energy band alignment of this heterostructure preserves light emission of MoS2 against nonradiative interlayer recombination processes and favors the charge transfer from MoS2, an n-type semiconductor, to FePS3, a p-type narrow-gap semiconductor. The strong depletion of carriers in the MoS2 layer is evidenced by a dramatic increase in the spectral weight of neutral excitons, which is strongly modulated by the thickness of the FePS3 underneath, leading to the increase of photoluminescence intensity. The present results demonstrate the potential for the rational design of van der Waals heterostructures with advanced optoelectronic properties.

Band Filling and Cross Quantum Capacitance in Ion-Gated Semiconducting Transition Metal Dichalcogenide Monolayers.

Ionic liquid gated field-effect transistors (FETs) based on semiconducting transition metal dichalcogenides (TMDs) are used to study a rich variety of extremely interesting physical phenomena, but important aspects of how charge carriers are accumulated in these systems are not understood. We address these issues by means of a systematic experimental study of transport in monolayer MoSe2 and WSe2 as a function of magnetic field and gate voltage, exploring accumulated densities of carriers ranging from approximately 1014 cm-2 holes in the valence band to 4 × 1014 cm-2 electrons in the conduction band. We identify the conditions when the chemical potential enters different valleys in the monolayer band structure (the K and Q valley in the conduction band and the two spin-split K-valleys in the valence band) and find that an independent electron picture describes the occupation of states well. Unexpectedly, however, the experiments show very large changes in the device capacitance when multiple valleys are occupied that are not at all compatible with the commonly expected quantum capacitance contribution of these systems, CQ = e2/ (dµ/dn). A theoretical analysis of all terms responsible for the total capacitance shows that under general conditions a term is present besides the usual quantum capacitance, which becomes important for very small distances between the capacitor plates. This term, which we call cross quantum capacitance, originates from screening of the electric field generated by charges on one plate from charges sitting on the other plate. The effect is negligible in normal capacitors but large in ionic liquid FETs because of the atomic proximity between the ions in the gate and the accumulated charges on the TMD, and it accounts for all our experimental observations. Our findings therefore reveal an important contribution to the capacitance of physical systems that had been virtually entirely neglected until now.

Highly Flexible and High-Performance Complementary Inverters of Large-Area Transition Metal Dichalcogenide Monolayers.

Complementary inverters constructed from large-area monolayers of WSe2 and MoS2 achieve excellent logic swings and yield an extremely high gain, large total noise margin, low power consumption, and good switching speed. Moreover, the WSe2 complementary-like inverters built on plastic substrates exhibit high mechanical stability. The results provide a path toward large-area flexible electronics.