The all-inorganic perovskite nanocrystals are currently in the research spotlight owing to their physical stability and superior optical properties—these features make them interesting for optoelectronic and photovoltaic applications. Here, we report on the observation of highly efficient carrier multiplication in colloidal CsPbI₃ nanocrystals prepared by a hot-injection method. The carrier multiplication process counteracts thermalization of hot carriers and as such provides the potential to increase the conversion efficiency of solar cells. We demonstrate that carrier multiplication commences at the threshold excitation energy near the energy conservation limit of twice the band gap, and has step-like characteristics with an extremely high quantum yield of up to 98%. Using ultrahigh temporal resolution, we show that carrier multiplication induces a longer build-up of the free carrier concentration, thus providing important insights into the physical mechanism responsible for this phenomenon. The evidence is obtained using three independent experimental approaches, and is conclusive.

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Carrier multiplication is a process in which one absorbed photon excites two or more electrons. This is of great promise to increase the efficiency of photovoltaic devices. Until now, the factors that determine the onset energy of carrier multiplication have not been convincingly explained. We show experimentally that the onset of carrier multiplication in lead chalcogenide quantum confined and bulk crystals is due to asymmetric optical transitions. In such transitions most of the photon energy in excess of the band gap is given to either the hole or the electron. The results are confirmed and explained by theoretical tight-binding calculations of the competition between impact ionization and carrier cooling. These results are a large step forward in understanding carrier multiplication and allow for a screening of materials with an onset of carrier multiplication close to twice the band gap energy. Such materials are of great interest for development of highly efficient photovoltaic devices.

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In semiconductor quantum dots (QDs), charge carrier cooling is in direct competition with carrier multiplication (CM), a process in which one absorbed photon excites two or more electrons that may improve the light conversion efficiency of photovoltaic devices. CM by an initially hot charge carrier occurs in competition with cooling, with the respective rates determining the CM efficiency. Until now, the factors that determine the onset energy and efficiency of CM have not been convincingly explained. Most research on cooling involves low photoexcitation energies close to the band gap, while the competition between CM and cooling takes place at higher energies where an electron or hole has an excess energy that is at least equal to the band gap. Moreover, CM rates have only been calculated theoretically, while experimental studies of CM have focused mostly on proving its occurrence in various materials. Understanding charge carrier cooling at high excess energy and comparing this to experimental CM rates is therefore of great interest. Chapters 2 and 3 of this thesis are aimed at understanding charge carrier cooling, while Chapters 4 and 5 relate this to the onset energy and efficiency of CM. The presented results are a large step forward in understanding cooling and CM and allow for a screening of materials with an onset of CM close to twice the band gap energy. Such materials are of great interest for development of highly efficient photovoltaic devices.@en

Understanding cooling of hot charge carriers in semiconductor quantum dots (QDs) is of fundamental interest and useful to enhance the performance of QDs in photovoltaics. We study electron and hole cooling dynamics in PbSe QDs up to high energies where carrier multiplication occurs. We characterize distinct cooling steps of hot electrons and holes and build up a broadband cooling spectrum for both charge carriers. Cooling of electrons is slower than of holes. At energies near the band gap we find cooling times between successive electronic energy levels in the order of 0.5 ps. We argue that here the large spacing between successive electronic energy levels requires cooling to occur by energy transfer to vibrational modes of ligand molecules or phonon modes associated with the QD surface. At high excess energy the energy loss rate of electrons is 1-5 eV/ps and exceeds 8 eV/ps for holes. Here charge carrier cooling can be understood in terms of emission of LO phonons with a higher density-of-states in the valence band than the conduction band. The complete mapping of the broadband cooling spectrum for both charge carriers in PbSe QDs is a big step toward understanding and controlling the cooling of hot charge carriers in colloidal QDs.

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In semiconductor quantum dots (QDs), charge carrier cooling is in direct competition with processes such as carrier multiplication or hot charge extraction that may improve the light conversion efficiency of photovoltaic devices. Understanding charge carrier cooling is therefore of great interest. We investigate high-energy optical transitions in PbSe QDs using hyperspectral transient absorption spectroscopy. We observe bleaching of optical transitions involving higher valence and conduction bands upon band edge excitation. The kinetics of rise of the bleach of these transitions after a pump laser pulse allow us to monitor, for the first time, cooling of hot electrons and hot holes separately. Our results show that holes cool significantly faster than electrons in PbSe QDs. This is in contrast to the common assumption that electrons and holes behave similarly in Pb chalcogenide QDs and has important implications for the utilization of hot charge carriers in photovoltaic devices.

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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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Luminescent copper indium sulfide (CIS) nanocrystals are a potential solution to the toxicity issues associated with Cd- and Pb-based nanocrystals. However, the development of high-quality CIS nanocrystals has been complicated by insufficient knowledge of the electronic structure and of the factors that lead to luminescence quenching. Here we investigate the exciton decay pathways in CIS nanocrystals using time-resolved photoluminescence and transient absorption spectroscopy. Core-only CIS nanocrystals with low quantum yield are compared to core/shell nanocrystals (CIS/ZnS and CIS/CdS) with higher quantum yield. Our measurements support the model of photoluminescence by radiative recombination of a conduction band electron with a localized hole. Moreover, we find that photoluminescence quenching in low-quantum-yield nanocrystals involves initially uncoupled decay pathways for the electron and hole. The electron decay pathway determines whether the exciton recombines radiatively or nonradiatively. The development of high-quality CIS nanocrystals should therefore focus on the elimination of electron traps.

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The cooling dynamics of hot charge carriers in colloidal lead chalcogenide nanocrystals is studied by white light transient absorption spectroscopy. We demonstrate a transient accumulation of charge carriers at a high-energy critical point in the Brillouin zone. Using a theoretical study of the cooling rate in lead chalcogenides, we attribute this slowing down of charge carrier cooling to a phonon scattering bottleneck around this critical point. Our approach allows for the first ever determination of hot carrier cooling rates, relevant in e.g. modeling of multiple exciton generation.@en