Lead selenide (PbSe) nanorods are of interest for applications in infrared LEDs, lasers, and photovoltaics due to the possibility of tuning their band gap from the far- to the near-infrared by decreasing their radius. We study the photogeneration quantum yield and properties of free charges and excitons in PbSe nanorods using a combination of time-resolved transient optical absorption and terahertz spectroscopy. Photoexcitation predominantly leads to the formation of excitons and to a smaller extent to free mobile charges. Theoretical analysis of the exprimental data yields an exciton polarizability of 10^-35 C m² V^-1. The sum of the mobilities of a free electron and a hole is found to be close to 100 cm² V^-1 s^-1. The high quantum yield of excitons makes PbSe nanorods of interest as a gain material in near-infrared LEDs or lasers. To use PbSe nanorods in photovoltaics, heterojunctions must be realized so that excitons can dissociate into free charges.

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Ultrathin two-dimensional (2D) materials have received much attention in the past years for a wide variety of photonic applications because of their pronounced room-temperature excitonic features, leading to unique properties in terms of light-matter interaction. However, only a few studies focus on light amplification and the complex photophysics at high excitation density. The beneficial nature of strong excitonic effects on optical gain remain hence unquantified, and despite the increased binding energies of the excitonic species, it remains unclear what the involvement of 2D excitons would be in optical gain. Here, we use colloidal CdSe nanoplatelets as a model system for colloidal 2D materials and show, using a quantitative and combinatory approach to ultrafast spectroscopy, that several excitation density-dependent optical gain regimes exist. At low density, optical gain originates from excitonic molecules delivering large material gains up to 20 000 cm ^-1 with an Auger limited lifetime of a few hundred picoseconds. At increasing pair density, we observe a persistence of this excitonic gain regime and the unexpected coexistence of blue-shifted and significantly enhanced optical gain up to 10 ⁵ cm ^-1 . We show that this peculiar situation originates from a carrier cooling bottleneck at high density that limits further exciton formation from unbound charge carriers. The insulating (multi-)exciton gas is found to coexist with the conductive phase, indicating the absence of a full Mott transition. Our results shed a new light on the photophysics of excitons in strongly excited 2D materials and pave the way for the development of more efficient (broadband) optical gain media and/or high exciton density applications.

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Two-dimensional electron-hole gases in colloidal semiconductors have a wide variety of applications. Therefore, a proper physical understanding of these materials is of great importance. In this paper we present a detailed theoretical analysis of the recent experimental results by Tomar et al. [J. Phys. Chem. C 123, 9640 (2019)1932-744710.1021/acs.jpcc.9b02085] that show an unexpected stability of excitons in CdSe nanoplatelets at high photoexcitation densities. Including the screening effects by free charges on the exciton properties, our analysis shows that CdSe nanoplatelets behave very differently from bulk CdSe, and in particular do not show a crossover to an electron-hole plasma in the density range studied experimentally, even though there is substantial overlap between the excitons at the highest densities achieved. From our results we also conclude that a quantum degenerate exciton gas is realized in the experiments, which opens the prospect of observing superfluidity in CdSe nanoplatelets in the near future.

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The aim of this thesis is to study the nature of photoexcitations and carrier multiplication in low-dimensional semiconductors using ultrafast spectroscopy techniques. Ongoing from a macroscopic scale to a nanoscale, the electronic and optical properties of a material become size dependent, and differ significantly from their bulk counterpart due to quantum confinement, and the surrounding dielectric environment. Electrons and holes in nano-semiconductors can attract each other to form neutral bound electron-hole pairs known as excitons. Stable robust excitons are useful to achieve optical gain and lasing. The Coulomb interaction between electrons and holes in nano-semiconductors is enhanced due to quantum confinement, which can lead to the creation of multiple electron-hole pairs per single absorbed photon via a process called carrier multiplication (CM). CM is beneficial to achieve a power conversion efficiency in a solar cell beyond the Shockley-Quiesser limit.@en

It has been shown recently that atomically coherent superstructures of a nanocrystal monolayer in thickness can be prepared by self-assembly of monodisperse PbSe nanocrystals, followed by oriented attachment. Superstructures with a honeycomb nanogeometry are of special interest, as theory has shown that they are regular 2-D semiconductors, but with the highest valence and lowest conduction bands being Dirac-type, that is, with a linear energy-momentum relation around the K-points in the zone. Experimental validation will require cryogenic measurements on single sheets of these nanocrystal monolayer superstructures. Here, we show that we can incorporate these fragile superstructures into a transistor device with electrolyte gating, control the electron density, and measure the electron transport characteristics at room temperature. The electron mobility is 1.5 ± 0.5 cm² V^-1 s^-1, similar to the mobility observed with terahertz spectroscopy on freestanding superstructures. The terahertz spectroscopic data point to pronounced carrier scattering on crystallographic imperfections in the superstructure, explaining the limited mobility.

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Carrier multiplication (CM) is a process in which a single photon excites two or more electrons. CM is of interest to enhance the efficiency of a solar cell. Until now, CM in thin films and solar cells of semiconductor nanocrystals (NCs) has been found at photon energies well above the minimum required energy of twice the band gap. The high threshold of CM strongly limits the benefits for solar cell applications. We show that CM is more efficient in a percolative network of directly connected PbSe NCs. The CM threshold is at twice the band gap and increases in a steplike fashion with photon energy. A lower CM efficiency is found for a solid of weaker coupled NCs. This demonstrates that the coupling between NCs strongly affects the CM efficiency. According to device simulations, the measured CM efficiency would significantly enhance the power conversion efficiency of a solar cell.

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We studied charge carrier photogeneration, cooling, carrier multiplication (CM) and charge mobility and decay in: a) isolated PbSe nanocrystals in solution, b) films of PbSe nanocrystals coupled by organic ligands, and c) 2D percolative networks of epitaxially connected PbSe nanocrystals. The studies were performed using ultrafast pump-probe spectroscopy with optical or terahertz/microwave conductivity detection. The effects of electronic coupling between the nanocrystals on charge mobility were characterized by frequency-resolved microwave and terahertz photoconductivity measurements. Reducing the size of ligand molecules between nanocrystals in a film strongly increases the charge mobility. Direct connection of nanocrystals in a percolative network yielded a sum of electron and hole mobilities as high as 270±10 cm²V^-1s^-1. We found that a high mobility is essential for multiple electron-hole pairs formed via CM to escape from recombination. The coupling between the nanocrystals was found to strongly affect the competition between cooling of hot charges by phonon emission and CM. In percolative networks of connected nanocrystals CM is much more efficient than in films with ligands between the nanocrystals. In the e networks CM occurs in a step-like fashion with threshold near the minimum photon energy of twice the band gap.

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All-printed transistors consisting of interconnected networks of various types of twodimensional nanosheets are an important goal in nanoscience. Using electrolytic gating, we demonstrate all-printed, vertically stacked transistors with graphene source, drain, and gate electrodes, a transition metal dichalcogenide channel, and a boron nitride (BN) separator, all formed from nanosheet networks.The BN network contains an ionic liquid within its porous interior that allows electrolytic gating in a solid-like structure. Nanosheet network channels display on:off ratios of up to 600, transconductances exceeding 5 millisiemens, and mobilities of >0.1 square centimeters per volt per second. Unusually, the on-currents scaled with network thickness and volumetric capacitance. In contrast to other devices with comparable mobility, large capacitances, while hindering switching speeds, allow these devices to carry higher currents at relatively low drive voltages.

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The implementation of next generation ultrathin electronics by applying highly promising dimensionality-dependent physical properties of two-dimensional (2D) semiconductors is ever increasing. In this context, the van der Waals layered semiconductor InSe has proven its potential as photodetecting material with high charge carrier mobility. We have determined the photogeneration charge carrier quantum yield and mobility in atomically thin colloidal InSe nanosheets (inorganic layer thickness 0.8-1.7 nm, mono/double-layers, ≤ 5 nm including ligands) by ultrafast transient terahertz (THz) spectroscopy. A near unity quantum yield of free charge carriers is determined for low photoexcitation density. The charge carrier quantum yield decreases at higher excitation density due to recombination of electrons and holes, leading to the formation of neutral excitons. In the THz frequency domain, we probe a charge mobility as high as 20 ± 2 cm²/(V s). The THz mobility is similar to field-effect transistor mobilities extracted from unmodified exfoliated thin InSe devices. The current work provides the first results on charge carrier dynamics in ultrathin colloidal InSe nanosheets.

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